Diselenoester electrolyte additives for fast charging lithium ion batteries

ABSTRACT

Lithium ion batteries and electrolytes therefor are provided, which include electrolyte additives having dithioester functional group(s) that stabilize the SEI (solid-electrolyte interface) at the surfaces of the anode material particles, and/or stabilize the CEI (cathode electrolyte interface) at the surfaces of the cathode material particles, and/or act as oxygen scavengers to prevent cell degradation. The electrolyte additives having dithioester functional group(s) may function as polymerization controlling and/or chain transfer agents that regulate the level of polymerization of other electrolyte components, such as VC (vinyl carbonate) and improve the formation and operation of the batteries. The lithium ion batteries may have metalloid-based anodes including mostly Si, Ge and/or Sn as anode active material particles.

BACKGROUND OF THE INVENTION 1. Technical Field

The present invention relates to the field of energy storage devices,and more particularly, to electrolytes and electrolyte additives forlithium ion batteries.

2. Discussion of Related Art

Lithium ion batteries are used for a growing range of applications, astheir safety and performance are improved. The electrolytes of lithiumion batteries are an important component that affects their safety andperformance.

SUMMARY OF THE INVENTION

The following is a simplified summary providing an initial understandingof the invention. The summary does not necessarily identify key elementsnor limit the scope of the invention, but merely serves as anintroduction to the following description.

One aspect of the present invention provides an electrolyte solution fora fast charging a lithium ion battery, comprising linear solventcomprising at least one four-carbon chain ester, cyclic carbonatesolvent comprising at least vinyl carbonate (VC) solvent, additives atan amount smaller than 5 wt %, and at least one lithium salt, whereinthe at least one four-carbon chain ester is represented by the structureof Formula (XVIa), Formula (XVIb) or any combination thereof:

whereinR^(45′) is a C₃-C₁₀ alkyl, C₃-C₂₀ alkyl or C₃-C₃₀ alkyl;R^(46′) is C₄-C₁₀ alkyl, C₄-C₂₀ alkyl or C₄-C₃₀ alkyl;R⁴⁸ is alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl orheteroaryl;R⁴⁹ is alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl orheteroaryl;each of the alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzylor heteroaryl of R⁸, R^(48′), R⁴⁹ or R^(49′) is optionally substitutedwith one or more of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic,heteroaryl, O—P(═O)(OR⁴⁸)₂, trihalomethyl, cyano, S(═O)—R⁴⁸, S(═O)₂—R⁴⁸,S(═O)₂—NR⁴⁸R⁴⁹, halide, cycloalkyl, alkoxy, nitro, NR⁴⁸R⁴⁹, C(O)NR⁴⁸R⁴⁹,N(R⁴⁸)C(═O)—R⁴⁹, hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol,C(═O)—OR⁴⁸, C(═O)—R⁴⁸, aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) orany combination thereof; and n is an integer between 0 and 10.

One aspect of the present invention provides lithium-ion batterieshaving electrolytes with additive(s) having dithioester (—C(═S)—S—),diselenoester (—C(═Se)—Se—), thioselenoester or selenothioester((—C(═S)—Se—) or (—C(═Se)—S—) functional group(s).

For example, one aspect of the present invention provides lithium ionbattery comprising: at least one anode comprising active material basedon Si, Ge and/or Sn, at least one cathode comprising active materialbased on at least one formulation comprising lithiumNickel-Manganese-Cobalt (NMC) and/or at least one formulation comprisingmodified Li-NMC (Li_(w)Ni_(x)Mn_(y)Co_(z)O₂) and/or at least oneformulation comprising LiMeO wherein Me comprises one or more of Ni, Co,Fe, Mn, Al and Li and O comprise one or more respective lithium andoxygen atoms, and/or at least one formulation comprising lithium NickelCobalt Aluminum oxide (NCA), and electrolyte comprising: solventcomprising at least one linear carbonate and/or ester and at least onecyclic carbonate and/or ester, at least one dissolved lithium salt, andat least one additive that is represented by Formula (I) and/or (Ib):

wherein:Z¹ is halide, alkyl, haloalkyl, aryl, alkenyl, alkynyl, cycloalkyl,heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy,NR¹R², P(═O)R¹R², benzyl, thiol, arylthiol, alkylthiol, heteroarylthiol,O(CH₂)_(n)C₄H₄S, amino pyridine, imidazole, cyclic amine, piperazine,N(CH₂CH₂)₂N—C(═S)—S—Z², a polymeric moiety or an oligomeric moiety;Z² is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, a polymeric moiety,CH(P(═O)(OR¹)₂)((C═O)OR²), CH₂C₆H₅, (CH₂)_(n)(CO)NR¹R², (CH₂)_(n)COOR¹,(CH₂)_(n)(CO)NH(C₅H₄N), (CH₂)_(n)SR¹, (CH₂)_(n)S(═O)R¹,(CH₂)_(n)S(═O)₂R¹,

an oligomeric moiety or S—C(═S)—Z¹;R¹-R² are each independently H, alkyl, haloalkyl, cycloalkyl, benzyl,aryl, heteroalicyclic, heteroaryl, polymeric moiety or an oligomericmoiety;each of the alkyl, haloalkyl, aryl, benzyl, alkenyl, alkynyl,cycloalkyl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, heteroaryloxy,polymeric moiety, oligomeric moiety arylthiol, alkylthiol orheteroarylthiol of Z¹, Z², R¹ or R² is optionally substituted with oneor more of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic,heteroaryl, O—P(═O)(OR¹)₂, trihalomethyl, S(═O)—R¹, S(═O)₂—R¹,S(═O)₂—NR¹R², halide, cycloalkyl, alkoxy, nitro, cyano, NR¹R²,C(O)NR¹R², N(R¹)C(═O)—R², hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR¹, C(═O)—R¹, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof; and n is an integer between0 and 10.

One aspect of the present invention provides a lithium ion batterycomprising: at least one anode comprising anode active material based onSi, Ge and/or Sn, at least one cathode comprising cathode activematerial based on at least one formulation comprising lithiumiron-phosphorus (LFP) oxide or lithium metal oxide (LiMeO), wherein Meis one or more metal selected from nickel, cobalt, manganese andaluminum and Li and O represent one or more respective lithium andoxygen atoms, and electrolyte comprising: solvent comprising at leastone linear carbonate and/or ester and at least one cyclic carbonateand/or ester, at least one dissolved lithium salt, and at least oneadditive that is represented by Formula (XIII), (XIV), (XV) or anycombination thereof:

wherein:Z⁴ is halide, alkyl, haloalkyl, aryl, alkenyl, alkynyl, cycloalkyl,heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy,NR⁴⁴R^(44′), P(═O)R⁴⁴R^(44′), benzyl, thiol, arylthiol, alkylthiol,heteroarylthiol, O(CH₂)_(n)C₄H₄S, amino pyridine, imidazole, cyclicamine, piperazine, N(CH₂CH₂)₂N—C(═S)—S—Z⁵, P(═O)(OR⁴⁴)₂, a polymericmoiety or an oligomeric moiety;Z⁵ is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, alkylthiol, S(═O)₂—R⁴⁴, S(═O)—R⁴⁴,S(═O)₂—NR⁴⁴R^(44′), a polymeric moiety, CH(P(═O)(OR⁴⁴)²)((C═O)OR^(44′)),CH₂C₆H₅, (CH₂)_(n)(CO)NR⁴⁴R^(44′), (CH₂)_(n)COOR⁴⁴,(CH₂)_(n)(CO)NH(C₅H₄N), (CH₂)_(n)SR¹, (CH₂)_(n)S(═O)R¹,(CH₂)_(n)S(═O)₂R¹,

an oligomeric moiety or S—C(═S)—Z⁴;R⁴⁴ and R^(44′) are each independently H, alkyl, haloalkyl, cycloalkyl,benzyl, aryl, heteroalicyclic, heteroaryl, polymeric moiety or anoligomeric moiety, wherein if nitrogen (N) is adjacent to R⁴⁴ andR^(44′) then R⁴⁴, R^(44′) and the adjacent nitrogen may form aheteroaryl or a heteroalicyclic ring;R⁴⁵ and R^(45′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl, wherein R⁴⁵, R^(45′) andthe adjacent nitrogen may form together a heteroaryl or heteroalicyclicring;R⁴⁶ and R^(46′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl;R⁴⁷ and R^(47′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl;each of the alkyl, haloalkyl, aryl, benzyl, alkenyl, alkynyl,cycloalkyl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, heteroaryloxy,polymeric moiety, oligomeric moiety arylthiol, alkylthiol orheteroarylthiol of Z⁴, Z⁵, R⁴⁴-R⁴⁷ or R^(44′)-R^(47′) is optionallysubstituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, O—P(═O)(OR⁴⁴)₂ or O—P(═O)(OR⁴⁵)₂,trihalomethyl, S(═O)—R⁴⁴ or S(═O)—R⁴⁵, C(═S)—O—R⁴⁴ or C(═S)—O—R⁴⁵,C(═O)—S—R⁴⁴ or C(═O)—S—R⁴⁵, S(═O)₂—R⁴⁴ or S(═O)₂—R⁴⁵, S(═O)₂—NR⁴⁴R^(44′)or S(═O)₂—NR⁴⁵R^(45′), halide, cycloalkyl, alkoxy, nitro, cyano,NR⁴⁴R^(44′) or NR⁴⁵R^(45′), C(O)NR⁴⁴R^(44′) or C(O)NR⁴⁵R^(45′),N(R⁴⁴)C(═O)—R^(44′) or N(R⁴⁵)C(═O)—R⁴⁵, hydroxy, alkylthiol, thiol,arylthiol, heteroarylthiol, C(═O)—OR⁴⁴ or C(═O)—OR⁴⁵, C(═O)—R⁴⁴ orC(═O)—R⁴⁵, aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) or anycombination thereof; andn is an integer between 0 and 10.

These, additional, and/or other aspects and/or advantages of the presentinvention are set forth in the detailed description which follows;possibly inferable from the detailed description; and/or learnable bypractice of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of embodiments of the invention and to showhow the same may be carried into effect, reference will now be made,purely by way of example, to the accompanying drawings in which likenumerals designate corresponding elements or sections throughout.

In the accompanying drawings:

FIG. 1 provides experimental results indicating improvements achieved byusing polymerization controlling agents as additives, according to someembodiments of the invention.

FIG. 2 provides a scatter plot of cycle life versus capacity for theexperimental results, according to some embodiments of the invention.

FIG. 3 provides a scatter plot of cell thickness versus cycle life forthe experimental results, according to some embodiments of theinvention.

FIG. 4 illustrates a typical charging/discharging curve withcorresponding voltage and current values over time, according to someembodiments of the invention.

FIG. 5 illustrates an improvement in cycling lifetime achieved by aphosphorane-based additive, according to some embodiments of theinvention.

FIG. 6 is a high-level flowchart illustrating a method, according tosome embodiments of the invention.

DETAILED DESCRIPTION OF THE INVENTION

In the following description, various aspects of the present inventionare described. For purposes of explanation, specific configurations anddetails are set forth in order to provide a thorough understanding ofthe present invention. However, it will also be apparent to one skilledin the art that the present invention may be practiced without thespecific details presented herein. Furthermore, well known features mayhave been omitted or simplified in order not to obscure the presentinvention. With specific reference to the drawings, it is stressed thatthe particulars shown are by way of example and for purposes ofillustrative discussion of the present invention only, and are presentedin the cause of providing what is believed to be the most useful andreadily understood description of the principles and conceptual aspectsof the invention. In this regard, no attempt is made to show structuraldetails of the invention in more detail than is necessary for afundamental understanding of the invention, the description taken withthe drawings making apparent to those skilled in the art how the severalforms of the invention may be embodied in practice.

Before at least one embodiment of the invention is explained in detail,it is to be understood that the invention is not limited in itsapplication to the details of construction and the arrangement of thecomponents set forth in the following description or illustrated in thedrawings. The invention is applicable to other embodiments that may bepracticed or carried out in various ways as well as to combinations ofthe disclosed embodiments. Also, it is to be understood that thephraseology and terminology employed herein are for the purpose ofdescription and should not be regarded as limiting.

Embodiments of the present invention provide efficient and economicalmethods and mechanisms for improving the cycling lifetime of lithium ionbatteries and thereby provide improvements to the technological field ofenergy storage.

Lithium ion batteries and electrolytes therefor are provided, whichinclude electrolyte additives having dithioester functional group(s)that stabilize the SEI (solid-electrolyte interface) at the surfaces ofthe anode material particles, and/or stabilize the CEI (cathodeelectrolyte interface) at the surfaces of the cathode material particles(possibly through oxidation of one or more of the disclosed additives),and/or act as scavengers of oxygen species to prevent or slow down celldegradation. The electrolyte additives having dithioester functionalgroup(s) may function as polymerization controlling and/or chaintransfer agents that regulate the level of polymerization of otherelectrolyte components, such as VC (vinyl carbonate) and improve theformation and operation of the batteries. The lithium ion batteries mayhave metalloid-based anodes including mostly Si, Ge and/or Sn as anodeactive material particles.

In various embodiments of lithium-ion batteries, e.g., in batterieshaving metalloid-based anode materials, electrolytes may compriseolefinic additives such as VC and/or olefin moieties which are formedin-situ during cell formation and cycling. Examples for electrolyte aredisclosed e.g., in U.S. Pat. No. 10,096,859, incorporated herein byreference in its entirety. In certain embodiments, electrolytes maycomprise a large proportion, e.g., 10%, 20%, 30% or more of VC and/orFEC as prominent cyclic carbonate compound, as disclosed e.g., in U.S.Pat. No. 10,199,677, incorporated herein by reference in its entirety.In certain embodiments, electrolytes may comprise linear solventcomprising at least one three-carbon and/or four-carbon chain ester,cyclic carbonate solvent and at least one lithium salt, as disclosede.g., in U.S. Patent Publication No. 2019/0148774, incorporated hereinby reference in its entirety.

During formation, olefins (of the olefin additives and/or of the olefinmoieties) polymerize to poly-olefins (in radical polymerization) and areattached to the anode as part of the SEI. “Polymerization controllingagents”, defined herein as compounds that control the chain length ofthe poly-olefins and/or stop olefin polymerization may be added to theelectrolyte. Non-limiting examples of polymerization controlling agentsinclude radical scavengers and chain transfer agents.

Radical scavenger(s), used as such polymerization controlling agent, maybe added to the electrolyte after the formation stage (at an electrolytereplenishment stage)—to stop olefin polymerization. For example, BHT(Butylated hydroxytoluene) and/or TEMPO((2,2,6,6-Tetramethylpiperidin-1-yl)oxyl) may be added to theelectrolyte after the formation stage.

Alternatively or complementarily, “chain transfer agents”, definedherein as compounds comprising a weak bond (e.g. —C(═S)—S—moiety, i.e. adithioester functional group) which facilitates a chain transferreaction (usually within a polymerization process/reaction) can be usedas polymerization controlling agents, to control chain length of thepoly-olefins. Non-limiting examples of chain transfer agents includedithioester compounds, thiols, haloalkanes (e.g. perfluoroiodoalkanes),organoselenium compounds (e.g. diphenyldiselenide), alkyl telluridecompounds, organostibine compounds and iniferter agents (whichsimultaneously act as initiators, transfer agents, and terminators; e.g.dithiocarbamate compounds). In some embodiments, non-limiting examplesof mechanisms involving the chain transfer agents include: reversibleaddition fragmentation chain transfer (RAFT, using e.g. the dithioestercompounds), iodine transfer polymerization (ITP, using e.g. theperfluoroiodoalkanes), Selenium-centered radical-mediated polymerization(using the organoselenium compounds), Telluride-mediated polymerization(TERP, using e.g. the alkyl telluride compounds), stibine mediatedpolymerization (using the organostibine compounds) and controlled freeradical iniferter polymerization (using iniferter agents).

Without being bound by any mechanism or theory, it is contemplated thatpolymerization controlling agents may be used to provide any of thefollowing advantages: (i) control the chain lengths/molecular weightsand distribution thereof, of the poly-olefins (e.g., poly-VC), (ii)prevent continuous occurrence of the reaction (which consumeselectrolyte, reduces the ionic conductivity of the electrolyte andreduces the electronic conductivity of the anode material particles),and related parasitic reactions. Specifically, chain transfer agents (orcomparable compounds and processes) and/or radical scavengers may beused to stop the polymerization at specified chain lengths that areoptimized with respect to battery operation and performance with respectto any of their cycle life, charging/discharging rates, safety and/orcapacity.

Without being bound by any mechanism or theory, at least some of thedisclosed compounds may improve the cycling lifetime by at least partlyproviding a passivation or protection layer on cathode active materialparticles and/or on the cathode, stabilizing the CEI cathode electrolyteinterface (e.g., possibly through oxidation of one or more of thedisclosed additives).

Without being bound by any mechanism or theory, at least some of thedisclosed compounds may oxidize before electrolyte components, anodecomponents and/or cathode components oxidize, and so provide protectionto any of these components. In certain embodiments, at least some of thedisclosed compounds may operate as oxygen scavengers, removing O₂ thatis left in the cell or that is being produced at small amounts duringthe operation of the cell before it damages other cell components.

It is noted that disclosed compounds may be used with cells comprisingany of the anode types and cathode types listed above, as well as withvarious electrolyte compositions.

The inventors suggest the following possible electrolyte additives thatmay be used as polymerization controlling agents, possibly withdifferent effective concentrations. In some embodiments, thepolymerization controlling agents are dithioester compounds that maycomprise molecules of the Formula (I):

wherein:Z¹ is halide, alkyl, haloalkyl, aryl, alkenyl, alkynyl, cycloalkyl,heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy,NR¹R², P(═O)R¹R², benzyl, thiol, arylthiol, alkylthiol, heteroarylthiol,O(CH₂)_(n)C₄H₄S, amino pyridine, imidazole, cyclic amine, piperazine,N(CH₂CH₂)₂N—C(═S)—S—Z², a polymeric moiety or an oligomeric moiety; Z²is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, a polymeric moiety,CH(P(═O)(OR¹)₂)((C═O)OR²), CH₂C₆H₅, (CH₂)_(n)(CO)NR¹R², (CH₂)_(n)COOR¹,(CH₂)_(n)(CO)NH(C₅H₄N), (CH₂)_(n)SR¹, (CH₂)_(n)S(═O)R¹,(CH₂)_(n)S(═O)₂R¹,

an oligomeric moiety or S—C(═S)—Z¹;R¹-R² are each independently H, alkyl, haloalkyl, cycloalkyl, benzyl,aryl, heteroalicyclic, heteroaryl, polymeric moiety or an oligomericmoiety. If nitrogen (N) is adjacent to R¹ and R² then R¹, R² and theadjacent nitrogen may form a heteroaryl or a heteroalicyclic ring;each of the alkyl, haloalkyl, aryl, benzyl, alkenyl, alkynyl,cycloalkyl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, heteroaryloxy,polymeric moiety, oligomeric moiety arylthiol, alkylthiol orheteroarylthiol of Z¹, Z², R¹ or R² is optionally substituted with oneor more of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic,heteroaryl, O—P(═O)(OR¹)₂, trihalomethyl, S(═O)—R¹, S(═O)₂—R¹,S(═O)₂—NR¹R², halide, cycloalkyl, alkoxy, nitro, cyano, NR¹R²,C(O)NR¹R², N(R¹)C(═O)—R², hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR¹, C(═O)—R¹, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof; and n is an integer between0 and 10.

In certain embodiments, Z² may be a carbon chain, e.g., alkyl,haloalkyl, aryl, alkenyl, alkynyl, a polymeric moiety having a carbonchain or an oligomeric moiety having a carbon chain.

In certain embodiments, Z¹ may be an electron donating group, e.g.,heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy,NR¹R², thiol, arylthiol, alkylthiol, heteroarylthiol, a polymeric moietywith an electron donating group or an oligomeric moiety with an electrondonating group.

In some embodiments, the dithioester compounds may comprise molecules ofthe Formula (Ia), (Iai), (Ic) or any combination thereof:

whereinR¹ and R² are each independently H, alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl, heteroaryl, polymeric moiety or an oligomericmoiety. If nitrogen (N) is adjacent to R¹ and R² then R¹, R² and theadjacent nitrogen may form a heteroaryl or a heteroalicyclic ring;R³ and R^(3′) are each independently H, alkyl, haloalkyl, alkenyl,alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy,O—P(═O)(OR¹)₂, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol,heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl, C(O)NR¹R²,NR¹R², N(R¹)C(═O)—R², C(═O)—OR¹, S(═O)—R¹, S(═O)₂—R¹ or S(═O)₂—NR¹R²;R⁴ is H, alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl orheteroaryl; each of the alkyl, haloalkyl, cycloalkyl, aryl, benzyl,heteroaryl, alkenyl, alkynyl, heteroalicyclic, alkoxy, alkylthiol,heteroarylthiol, aryloxy, heteroaryloxy or arylthiol of R¹, R², R³,R^(3′) or R⁴ is optionally substituted with one or more of alkyl,haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR¹)₂,trihalomethyl, cyano, S(═O)—R¹, S(═O)₂—R¹, S(═O)₂—NR¹R², halide,cycloalkyl, alkoxy, nitro, NR¹R², C(O)NR¹R², N(R¹)C(═O)—R², hydroxy,alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR¹, C(═O)—R¹,aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) or any combinationthereof; andn is an integer between 0 and 10.

In certain embodiments, the dithioester compounds may comprise moleculesof Formula (Iai), wherein R³ and R^(3′) are H and R¹-R² and R⁴ aredescribed hereinabove. In certain embodiments, the dithioester compoundsmay comprise molecules of Formula (Ia), (Iai) as described hereinaboveor any combination thereof.

In any of the disclosed embodiments, the double-bonded sulfur may be atleast partly replaced be selenium, with additives including, at leastpartly, molecules of the Formula (Ib):

wherein:Z¹ is halide, alkyl, haloalkyl, aryl, alkenyl, alkynyl, cycloalkyl,heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy,NR¹R², P(═O)R¹R², benzyl, thiol, arylthiol, alkylthiol, heteroarylthiol,O(CH₂)_(n)C₄H₄S, amino pyridine, imidazole, cyclic amine, piperazine,N(CH₂CH₂)₂N—C(═S)—S—Z², a polymeric moiety or an oligomeric moiety; Z²is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, a polymeric moiety,CH(P(═O)(OR¹)₂)((C═O)OR²), CH₂C₆H₅, (CH₂)_(n)(CO)NR¹R², (CH₂)_(n)COOR¹,(CH₂)_(n)(CO)NH(C₅H₄N), (CH₂)_(n)SR¹, (CH₂)_(n)S(═O)R¹,(CH₂)_(n)S(═O)₂R¹,

an oligomeric moiety or S—C(═S)—Z¹;R¹-R² are each independently H, alkyl, haloalkyl, cycloalkyl, benzyl,aryl, heteroalicyclic, heteroaryl, polymeric moiety or an oligomericmoiety. If nitrogen (N) is adjacent to R¹ and R² then R¹, R² and theadjacent nitrogen may form a heteroaryl or a heteroalicyclic ring; eachof the alkyl, haloalkyl, aryl, benzyl, alkenyl, alkynyl, cycloalkyl,heteroaryl, heteroalicyclic, alkoxy, aryloxy, heteroaryloxy, polymericmoiety, oligomeric moiety arylthiol, alkylthiol or heteroarylthiol ofZ¹, Z², R¹ or R² is optionally substituted with one or more of alkyl,haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR¹)₂,trihalomethyl, S(═O)—R¹, S(═O)₂—R¹, S(═O)₂—NR¹R², halide, cycloalkyl,alkoxy, nitro, cyano, NR¹R², C(O)NR¹R², N(R¹)C(═O)—R², hydroxy,alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR¹, C(═O)—R¹,aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) or any combinationthereof; and n is an integer between 0 and 10.

In some embodiments, the dithioester compounds may comprise molecules ofthe Formula (II):

whereinZ¹ is halide, alkyl, haloalkyl, aryl, alkenyl, alkynyl, cycloalkyl,heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy,NR¹R², P(═O)R¹R², benzyl, thiol, arylthiol, alkylthiol, heteroarylthiol,O(CH₂)_(n)C₄H₄S, amino pyridine, imidazole, cyclic amine, piperazine,N(CH₂CH₂)₂N—C(═S)—S—Z², a polymeric moiety or an oligomeric moiety; Z²is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, a polymeric moiety,CH(P(═O)(OR)₂)((C═O)OR), CH₂C₆H₅, (CH₂)_(n)(CO)NR¹R²,(CH₂)_(n)(CO)NH(C₅H₄N), (CH₂)_(n)SR¹, (CH₂)_(n)S(═O)R¹,(CH₂)_(n)S(═O)₂R¹,

an oligomeric moiety or S—C(═S)—Z¹;R¹ and R² are each independently H, alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl, heteroaryl, polymeric moiety or an oligomericmoiety. If nitrogen (N) is adjacent to R¹ and R² then R¹, R² and theadjacent nitrogen may form a heteroaryl or a heteroalicyclic ring;each of the alkyl, haloalkyl, cycloalkyl, aryl, benzyl, heteroaryl,alkenyl, alkynyl, heteroalicyclic, alkoxy, alkylthiol, heteroarylthiol,aryloxy, heteroaryloxy or arylthiol of Z¹, Z², R¹ or R² is optionallysubstituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, O—P(═O)(OR¹)₂, trihalomethyl, cyano,S(═O)—R¹, S(═O)₂—R¹, S(═O)₂—NR¹R², halide, cycloalkyl, alkoxy, nitro,NR¹R², C(O)NR¹R², N(R¹)C(═O)—R², hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR¹, C(═O)—R¹, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof;L is a linker; and n is an integer between 0 and 10.

In some embodiments, the dithioester compounds may comprise molecules ofthe Formula (Ha):

whereinR¹ and R² are each independently H, alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl, heteroaryl, polymeric moiety or an oligomericmoiety. If nitrogen (N) is adjacent to R¹ and R² then R¹, R² and theadjacent nitrogen may form a heteroaryl or a heteroalicyclic ring;R³ is H, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl,heteroalicyclic heteroaryl, alkoxy, hydroxy, O—P(═O)(OR¹)₂, thiol,alkylthiol, aryloxy, heteroaryloxy, arylthiol, heteroarylthiol, nitro,halide, trihalomethyl, cyano, benzyl, C(O)NR¹R², NR¹R², N(R¹)C(═O)—R²,C(═O)—OR¹, S(═O)—R¹, S(═O)₂—R¹ or S(═O)₂—NR¹R²;each of the alkyl, haloalkyl, cycloalkyl, aryl, benzyl, heteroaryl,alkenyl, alkynyl, heteroalicyclic, alkoxy, alkylthiol, heteroarylthiol,aryloxy, heteroaryloxy or arylthiol of R¹, R² or R³ is optionallysubstituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, O—P(═O)(OR¹)₂, trihalomethyl, cyano,S(═O)—R¹, S(═O)₂—R¹, S(═O)₂—NR¹R², halide, cycloalkyl, alkoxy, nitro,NR¹R², C(O)NR¹R², N(R¹)C(═O)—R², hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR¹, C(═O)—R¹, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof; L is a linker; and n each isindependently an integer between 0 and 10.

In some embodiments, the dithioester compounds may comprise molecules ofthe Formula (IIb):

whereinR¹ and R² are each independently H, alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl, heteroaryl, polymeric moiety or an oligomericmoiety. If nitrogen (N) is adjacent to R¹ and R² then R¹, R² and theadjacent nitrogen may form a heteroaryl or a heteroalicyclic ring;R³ is H, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl,heteroalicyclic heteroaryl, alkoxy, hydroxy, O—P(═O)(OR¹)₂, thiol,alkylthiol, aryloxy, heteroaryloxy, arylthiol, heteroarylthiol, nitro,halide, trihalomethyl, cyano, benzyl, C(O)NR¹R², NR¹R², N(R¹)C(═O)—R²,C(═O)—OR¹, S(═O)—R¹, S(═O)₂—R¹ or S(═O)₂—NR¹R²;each of the alkyl, haloalkyl, cycloalkyl, aryl, benzyl, heteroaryl,alkenyl, alkynyl, heteroalicyclic, alkoxy, alkylthiol, heteroarylthiol,aryloxy, heteroaryloxy or arylthiol of R¹, R² or R³ is optionallysubstituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, O—P(═O)(OR¹)₂, trihalomethyl, cyano,S(═O)—R¹, S(═O)₂—R¹, S(═O)₂—NR¹R², halide, cycloalkyl, alkoxy, nitro,NR¹R², C(O)NR¹R², N(R¹)C(═O)—R², hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR¹, C(═O)—R¹, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof;m is an integer between 1 and 10,000; andn each is independently an integer between 0 and 10.

In some embodiments, non-limiting examples of dithioester compoundsinclude the following:

whereinm is an integer between 1 and 10,000.

As a non-limiting example of a polymerization controlling agent, theadditive 1a, may be used in the electrolyte.

It is emphasized that disclosed embodiments and the results are notbound by theory and are not limited to the operation mechanism of thedisclosed additives as a polymerization controlling agent. In variousembodiments, any of the disclosed additives may be advantageous, e.g.,for increasing the cycling lifetime of the respective batteries throughany of a range of surface reactions involved in the process of the SEI(solid electrolyte interphase) layer, so that any of the disclosedadditives may at least partly be used as an SEI-forming additive.Alternatively or complementarily, any of the disclosed additives may atleast partly decompose and any of its decomposition products may beoperative as an SEI-forming additive. In various embodiments, any of thedisclosed additives may be advantageous, e.g., in modifying electrolytecomponents in a different way than through the chain transfer mechanism,e.g., reacting with double bonds in electrolyte components such as VCand/or olefins, and/or by affecting reaction products of electrolytecomponents during SEI formation and/or with SEI components, e.g., bypromoting polymerization of double bonds to change the chemicalcomposition of the electrolyte and/or of the SEI. In certainembodiments, any of the disclosed additives and/or their decompositionproducts and/or related compounds may be advantageous, e.g., forpreventing or attenuating various parasitic reactions (via degenerativeradical state) in the electrolyte and/or in the SEI during batteryformation and/or operation. In certain embodiments, any of the disclosedadditives and/or related compounds may be advantageous, e.g., forscavenging various by-products of the reactions in the operatingbattery, such operating as an H₂O/HF scavenger. In certain embodiments,any of the disclosed additives and/or related compounds may beadvantageous in electrochemical processes, in addition or in place oftheir advantages in chemical processes. For example, any of thedisclosed additives and/or related compounds may affect the surfacepotential and/or the voltage during cell operation, and increase thecell cycling lifetime through electrochemical effects.

Various embodiments comprise new additive structures based on Formula Iand/or additive structures with added functional groups and/orapplication of various additives in energy storage devices such aslithium ion batteries. Disclosed additives may be used in theelectrolyte of the batteries in liquid and/or solid form. One or more ofthe disclosed additives may be added to any form of electrolyte, such assolid, gel, liquid and/or polymeric electrolytes, with correspondingsolvents. In various embodiments, one or more of the disclosed additivesmay be added to the cathode and/or to the anode, possibly in addition totheir use in the electrolyte. In various embodiments, two or more of thedisclosed additives may be used in combination, in any of the disclosedembodiments (e.g., in the same or in different components of thebattery, in same or in different states, applied in same or in differentstages of battery production, etc.).

In some embodiments, the additives are represented by Formula (I):

whereinZ² is (CH₂)_(n)(CO)NR¹R², (CH₂)_(n)SR¹, (CH₂)_(n)S(═O)R¹,(CH₂)_(n)S(═O)₂R¹, or

and Z¹ is NR¹R², cyclic amine, piperazine and N(CH₂CH₂)₂N—C(═S)—S—Z²,and where n, R¹ and R² are as defined hereinabove.

In some embodiments, Z² is (CH₂)_(n)(CO)NR¹R²; and Z¹ is NR¹R². Inanother embodiment, Z² is (CH₂)_(n)(CO)N(CH₃)₂ and Z¹ is NR¹R²; and theadditives may comprise:

In some embodiments, Z¹ is NR′R² and Z² is (CH₂)_(n)SR¹,(CH₂)_(n)S(═O)R¹ or (CH₂)_(n)S(═O)₂R¹; and the additives may comprise:

In some embodiments, the additives are represented by Formula (Id):

wherein n and Z¹ are as defined hereinabove. In one embodiment, Z¹ isNR¹R². In certain embodiments, disclosed additives may comprise any ofthe following structures and/or

variations and substitutions thereof.

Concerning compound 36, the inventors note that using 0.6% of compound36 as additive increased the cycling lifetime ca. threefold (˜330%), andusing compounds 1a or 35 as additives increased the cycling lifetime ca.twofold (˜230%). Accordingly, in any of disclosed electrolytes, one ormore of compounds 1a, 35 and/or 46 may be added.

In some embodiments, the N,N-Dimethyl acetamide functional group of theabove compounds possibly forms a complex with the Lewis acid PF₅ whichis produced by the thermal dissociation of LiPF₆ and possibly preventsthe decomposition of electrolytes in lithium ion batteries.Alternatively or complimentarily, the same or corresponding functionalgroups may be used to prevent decomposition of electrolytes with othertypes of lithium salt.

In some embodiments, the additives are represented by Formula (I):

whereinZ² is (CH₂)_(n)(CO)NR¹R² or (CH₂)_(n)(CO)NH(C₅H₄N), and Z¹ is NR¹R²,imidazole or amino pyridine, and where n, R¹ and R² are as definedhereinabove. In some embodiments, the imidazole ring or amino pyridineof Z¹ is possibly involved in HF scavenging when applied in lithium ionbatteries. Alternatively or complimentarily, the same or correspondingfunctional groups may be used to prevent decomposition of electrolyteswith other types of lithium salt. In certain embodiments, disclosedadditives may comprise the following structure and/or variations andsubstitutions thereof:

In some embodiments, the additives are represented by Formula (I):

whereinZ² is (CH₂)_(n)C₆H₅, and Z¹ is O(CH₂)_(n)C₄H₄S, and where n is definedhereinabove.In some embodiments, the thiophene functional group of Z¹ is possiblydecomposed and/or polymerized on the electrode's surface prior to theintroduction of electrolyte, possibly forming a conducting protectivelayer and preventing electrolyte decomposition when applied in lithiumion batteries. In certain embodiments, disclosed additives may comprisethe following structure and/or variations and substitutions thereof:

In some embodiments, the additives are represented by Formula (I):

whereinZ² is CH(P(═O)(OR¹)₂)((C═O)OR²), and Z¹ is NR¹R², and where R¹ and R²are as defined hereinabove. In certain embodiments, disclosed additivesmay comprise the following structure and/or variations and substitutionsthereof:

In some embodiments, when applied in lithium ion batteries, the oxygenof the phosphate functional group may have the ability to neutralize PF₅through (Lewis) acid-base coordination, and/or the phosphate functionalgroup may function as a fire retardant, terminating the radicalpropagation in the combustion process. Alternatively or complimentarily,the same or corresponding functional groups may be used to preventdecomposition of electrolytes with other types of lithium salt.

In certain embodiments, disclosed additives may comprise any of thefollowing structures and/or variations and substitutions thereof:

In various embodiments, compound 44 and/or variations and/orsubstitutions thereof may be used for chelation of metals when appliedin lithium ion batteries. In various embodiments, compound 45 and/orvariations and/or substitutions thereof may be used for covalent bindingto Si (or possibly Ge and/or Sn), when applied in lithium ion batteries.In various embodiments, compound 46 and/or variations and/orsubstitutions thereof may be used for improving the ionic conductivityin any of the cell components, when applied in lithium ion batteries. Invarious embodiments, compound 47 and/or variations and/or substitutionsthereof may be used for forming SEI (solid electrolyte interphase) onthe anode(s) and/or CEI (cathode electrolyte interphase) on thecathode(s), when applied in lithium ion batteries. In variousembodiments, compound 48 and/or variations and/or substitutions thereofmay be used for scavenging HF when applied in lithium ion batteries. Invarious embodiments, end double bonds of compounds 49, 50 and/orvariations and/or substitutions thereof may be used for polymerizationof disclosed additive(s), see, e.g., below, when applied in lithium ionbatteries. In various embodiments, the end triple bond of compound 51and/or variations and/or substitutions thereof may be used forpolymerization of disclosed additive(s), see, e.g., below, when appliedin lithium ion batteries. In various embodiments, compound 52 and/orvariations and/or substitutions thereof may be used to providedi-functional additives as an example for multi-arm additives (e.g.,RAFT additives), see, e.g., below, when applied in lithium ionbatteries. In various embodiments, compound 53 and/or variations and/orsubstitutions thereof may be used to provide tri-functional additives asan example for multi-arm additives (e.g., RAFT additives), see, e.g.,below, when applied in lithium ion batteries. In various embodiments,compound 54 and/or variations and/or substitutions thereof may be usedto provide tetra-functional additives as an example for multi-armadditives (e.g., RAFT additives), see, e.g., below, when applied inlithium ion batteries. In various embodiments, compound 55 and/orvariations and/or substitutions thereof comprise a sultone functionalgroup that may be used to support SEI formation, when applied in lithiumion batteries.

In various embodiments, disclosed additives may comprise any of thefollowing structures and/or variations and substitutions thereof, e.g.,as RAFT structures:

It is noted that while structures of some of the disclosed compounds,e.g., compounds 37, 49, 50, 56-58, 60, 61, 63 and 64 may be known, theirapplication in lithium ion batteries, e.g., in electrolytes thereof,were found by the inventors to be surprisingly beneficial. Moreover,modification of disclosed compounds may also be beneficial in theirapplication in lithium ion batteries, e.g., in electrolytes thereof.

In various embodiments, disclosed additives may be applied in lithiumion batteries having metalloid-based anodes, e.g., having activematerial particles with Si, Ge and/or Sn. In various embodiments,disclosed additives may be applied in lithium ion batteries havingcarbon-based anodes, e.g., having graphite active material particlesand/or possibly active material particles with graphene or other carbonforms.

In some embodiments, the dithioester compounds are polymeric, oligomericor dendritic compounds comprising a polymeric, oligomeric or dendrimericcore and multiple dithioester moieties “arms” attached to the core, asmay be represented by Formula (Ma) or (Mb):

whereinthe core is a dendritic, oligomeric or polymeric moiety, e.g., having acarbon chain such as polyamide chains, polyester chains, or polyethylenechains;Z¹ is halide, alkyl, haloalkyl, aryl, alkenyl, alkynyl, cycloalkyl,heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy,NR¹R², P(═O)R¹R², benzyl, thiol, arylthiol, alkylthiol, heteroarylthiol,a polymeric moiety or an oligomeric moiety;Z² is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, a polymeric moiety,CH(P(═O)(OR¹)₂)((C═O)OR²), CH₂C₆H₅, (CH₂)_(n)(CO)NR¹R². (CH₂)_(n)COOR¹,(CH₂)_(n)(CO)NH(C₅H₄N), (CH₂)_(n)SR¹, (CH₂)_(n)S(═O)R¹, (CH₂)S(═O)₂R¹,

an oligomeric moiety or S—C(═S)—Z¹;R¹ and R² are each independently H, alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl, heteroaryl, polymeric moiety or an oligomericmoiety. If nitrogen (N) is adjacent to R¹ and R² then R¹, R² and theadjacent nitrogen may form a heteroaryl or a heteroalicyclic ring;each of the alkyl, haloalkyl, cycloalkyl, aryl, benzyl, heteroaryl,alkenyl, alkynyl, heteroalicyclic, alkoxy, alkylthiol, heteroarylthiol,aryloxy, heteroaryloxy or arylthiol of Z¹, Z², R¹ or R² is optionallysubstituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, O—P(═O)(OR¹)₂, trihalomethyl, cyano,S(═O)—R¹, S(═O)₂—R¹, S(═O)₂—NR¹R², halide, cycloalkyl, alkoxy, nitro,NR¹R², C(O)NR¹R², N(R¹)C(═O)—R², hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR¹, C(═O)—R¹, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof;p is an integer between 1 and 1000; andn is an integer between 0 and 10.

In certain embodiments, p of Formula (Ma) and (Mb) may be 1 or 2.

In various embodiments, the double-bonded sulfur may be replaced byselenium.

In some embodiments, the polymeric, oligomeric or dendritic compoundsare represented by the following non-limiting examples:

In some embodiments, the additives are represented by Formula (IVa) or(IVb):

whereinZ¹ is halide, alkyl, haloalkyl, aryl, alkenyl, alkynyl, cycloalkyl,heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy,NR¹R², P(═O)R¹R², benzyl, thiol, arylthiol, alkylthiol, heteroarylthiol,O(CH₂)_(n)C₄H₄S, amino pyridine, imidazole, cyclic amine, piperazine,N(CH₂CH₂)₂N—C(═S)—S—Z², a polymeric moiety or an oligomeric moiety; Z²is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, a polymeric moiety,CH(P(═O)(OR¹)₂)((C═O)OR²), CH₂C₆H₅, (CH₂)_(n)(CO)NR¹R², (CH₂)_(n)COOR¹,(CH₂)_(n)(CO)NH(C₅H₄N), (CH₂)_(n)SR¹, (CH₂)_(n)S(═O)R¹,(CH₂)_(n)S(═O)₂R¹,

an oligomeric moiety or S—C(═S)—Z¹;R¹ and R² are each independently H, alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl, heteroaryl, polymeric moiety or an oligomericmoiety. If nitrogen (N) is adjacent to R¹ and R² then R¹, R² and theadjacent nitrogen may form a heteroaryl or a heteroalicyclic ring;each of the alkyl, haloalkyl, cycloalkyl, aryl, benzyl, heteroaryl,alkenyl, alkynyl, heteroalicyclic, alkoxy, alkylthiol, heteroarylthiol,aryloxy, heteroaryloxy or arylthiol of Z¹, Z², R¹ or R² is optionallysubstituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, O—P(═O)(OR¹)₂, trihalomethyl, cyano,S(═O)—R¹, S(═O)₂—R¹, S(═O)₂—NR¹R², halide, cycloalkyl, alkoxy, nitro,NR¹R², C(O)NR¹R², N(R¹)C(═O)—R², hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR¹, C(═O)—R¹, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof;n is an integer between 0 and 10;n¹ is an integer between 1 and 3;n² is 3 or 4;M¹ is a metal selected from Si, Ti, Zr and Al;if M¹ is Si, Ti or Zr then n¹ is an integer between 1-3 and n² is 4;if M¹ is Al then n¹ 1 or 2 and n² is 3; andL is a linker.

Alternative known chain transfer agents and corresponding modificationsmay also be used to achieve increased cycling lifetime of the respectivecells.

In certain embodiments, cells with high VC proportion and polymerizationcontrolling agents were shown to increase cycling lifetime of therespective cells by 50-100%, providing a significant progress in thefield of fast charging lithium ion batteries. For example, the resultspresented below indicate the efficiency of polymerization controllingagents in this respect.

FIG. 1 provides experimental results indicating improvements achieved byusing polymerization controlling agents as additives, according to someembodiments of the invention. The experiment was designed to containfour groups with different concentrations of polymerization controllingagents as additives. The first group, composed of three full cells,served as control, running at default parameters (1Ah cells, 6.5 ml ofelectrolyte composed of 3/3.5/3.5 of VC(vinylene carbonate)/EB(ethylbutyrate)/BA(butyl acetate) and 1M LiPF₆, same formation and cyclingschemes, see e.g., below, and 15bar pressure applied to the pouches overmetal plates) with no polymerization controlling agents as inhibitors.In the other three groups, each containing six full cell pouches (and anadditional pouch that is run for half the cycling lifetime, used forunderstanding the degradation mechanisms), three different electrolyteconcentrations of polymerization controlling agents as additives wereused, namely 0.15%, 0.57% and 1.1%. The electrolyte was filled in twosteps, before formation 5.6 ml of electrolyte were filled, with noinhibitors, for all groups, and after degassing additional 0.9 ml ofelectrolyte were added, with inhibitor concentration calculated togenerate the final desired concentrations listed above. Other runningparameters were the standard “zero-series” for all cells. The cells wereassembled with standard parameters in C:A ratio range of 1.01-0.95, andcalculated capacity range of 2178-2103 mAh and 6.5 ml of 3/3.5/3.5VC/EB/BA electrolyte. In the formation procedure, the cells were chargedup to 4V, at varying currents (typically starting at a very low currentthat corresponds to a charging rate of C/1000 and increasing the currentas the cell charges and the voltage rises, carried out similarly for allcells), following a discharge at C/10 down to 3V. The first cycle wasfollowing by four cycles of CCCV (constant current followed by constantvoltage) charging to 4V and discharging to 3V, both at C/2. The cycleswere performed under plates with applied pressure of 15bar and completedwith degassing and addition of 0.9 ml of electrolyte with additiveconcentration calculated to generate the final desired concentration asdisclosed above. Standard cycling was performed with CCCV charging at 8Cup to 4.3V and discharging down to 3V. The voltage range and thecharging rate were adjusted according to the capacity retention percentuntil EoL (end of life) was reached at 80% retention.

The formation procedure was similar for the four groups, prior to theaddition of the polymerization controlling agent. It was found that theaddition of the polymerization controlling agent decreased the high Ccapacity in a gradual manner as illustrated in the figure below, yeteven the cells in the highest polymerization controlling agentconcentration run in a capacity within the spec (>51.5%). The differenthigh C capacity was taken into account in the cycle life comparisonpresented below, as it is known that even a few percent difference hasan effect on cycling.

The low volumetric energy density observed on the highest polymerizationcontrolling agent concentration (1.1%) may be understood as a result ofboth the lower 10C capacity and the larger thickness of the cells asdescribed above.

FIG. 2 provides a scatter plot of cycle life versus capacity for theexperimental results, according to some embodiments of the invention. Itis noted that the medium polymerization controlling agent concentrationgroup (0.57%) yielded the best results in terms of cycling rate andcycling lifetime. The group of cells with the highest polymerizationcontrolling agent concentration (1.1%) seems to present betterperformance than the control cell group (0%) and the low polymerizationcontrolling agent concentration groups (0.15%), which display similarperformances with relatively low cycling lifetime. However, presentlybut no direct comparison is enabled due to capacity difference andpossibly other differences.

FIG. 3 provides a scatter plot of cell thickness versus cycle life forthe experimental results, according to some embodiments of theinvention. The results show that cells with the medium polymerizationcontrolling agent concentration (0.57%) swelled less than cells with thehigher polymerization controlling agent concentration (1.1%), and bothgroups ran a similar and larger number cycles than cells from the twoother groups that swelled less (and are not directly comparable withregard to swelling). In a detailed examination of the individual poucheswith respect to the number of cycles indicates no specific effect of theaddition of polymerization controlling agent on the swelling of thepouches.

In conclusion, pouches with the medium and high polymerizationcontrolling agent concentration of 0.57% and 1.1% displayed considerablylonger cycling lifetimes, by ca. 55%, compared to the control group(without polymerization controlling agents) and compared to the groupwith lower polymerization controlling agent concentration (0.15%). Thegroup with medium polymerization controlling agent concentration (0.57%)exhibited higher capacity than the group with high polymerizationcontrolling agent concentration (1.1%).

In an experimental setting, coin cells were used to compare performancewith different additives. The anode was a Si-based anode with aNMC-based cathode. The baseline electrolyte included vinyl carbonate,butyl acetate and ethyl butyrate. This electrolyte was compared toelectrolytes with additives (listed in Table 1 below), numberedaccording to the disclosure above. The cycle life was measured byrunning the coin cells by 10C (6 minutes) charge and 1C (60 minutes)discharge. FIG. 4 illustrates a typical charging/discharging curve withcorresponding voltage and current values over time, according to someembodiments of the invention. All the experiments were conducted on atleast five coin cells each, with the average cycle life shown in Table1.

TABLE 1 Comparison of performance with different additives ElectrolyteAverage Cycle life Baseline 171 With additive 12a 302 With additive 1b265 With additive 9 234 With additive 11 215 With additive 2 274 Withadditive 3 218 With additive 57 217 With additive 15 215 With additive18 260 With additive 35 320 With additive 59 290 With both additives, 35and 59 339

It is clearly seen that an increase of cycle life has been achievedusing the disclosed additives. It is noted that no tradeoffs in energydensity or average or nominal voltage were observed in comparison to thebaseline sample.

In particular, additives 9, 18, 1b, 2, 59, 12a and 35 (reproducedbelow), as well as combinations thereof (exemplified on the combinationof additives 35 and 59) have been shown to increase the cycling lifetimeby 50-100%.

In various embodiments, any of the following related additives may beused in the electrolytes:

wherein R¹⁰³, R¹⁰⁴ and R¹⁰⁵ are each independently H, alkyl, haloalkyl,alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy,hydroxy, O—P(═O)(OR¹)₂, thiol, alkylthiol, aryloxy, heteroaryloxy,arylthiol, heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR¹R², NR¹R², N(R¹)C(═O)—R², C(═O)—OR¹, S(═O)—R¹, S(═O)₂—R¹ orS(═O)₂—NR¹R²;

wherein each of the alkyl, haloalkyl, cycloalkyl, aryl, benzyl,heteroaryl, alkenyl, alkynyl, heteroalicyclic, alkoxy, alkylthiol,heteroarylthiol, aryloxy, heteroaryloxy or arylthiol of R¹, R², R¹⁰³,R¹⁰⁴ and R¹⁰⁵ is optionally substituted with one or more of alkyl,haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR¹)₂,trihalomethyl, cyano, S(═O)—R¹, S(═O)₂—R¹, S(═O)₂—NR¹R², halide,cycloalkyl, alkoxy, nitro, NR¹R², C(O)NR¹R², N(R¹)C(═O)—R², hydroxy,alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR¹, C(═O)—R¹,aryl, aryloxy, heteroaryloxy or any combination thereof, and/or with R¹and R² as defined hereinabove;

n³ each is independently an integer between 0 and 10; and

n each is independently an integer between 0 and 10.

In some embodiments, the electrolytic additives are represented by thestructure of Formula (V):

WhereinR⁵-R⁷ are each independently H, alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl or heteroaryl;R⁸ is H, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl,heteroalicyclic heteroaryl, alkoxy, hydroxy, O—P(═O)(OR⁵)₂, thiol,alkylthiol, aryloxy, heteroaryloxy, arylthiol, heteroarylthiol, nitro,halide, trihalomethyl, cyano, benzyl, C(O)NR⁵R⁶, NR⁵R⁶, N(R⁵)C(═O)—R⁶,C(═O)—OR⁵, S(═O)—R⁵, S(═O)₂—R⁵ or S(═O)₂—NR⁵R⁶;R⁹ is H, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl,heteroalicyclic heteroaryl, alkoxy, hydroxy, O—P(═O)(OR⁵)₂, thiol,alkylthiol, aryloxy, heteroaryloxy, arylthiol, heteroarylthiol, nitro,halide, trihalomethyl, cyano, benzyl, C(O)NR⁵R⁶, NR⁵R⁶, N(R⁵)C(═O)—R⁶,C(═O)—OR⁵, S(═O)—R⁵, S(═O)₂—R⁶ or S(═O)₂—NR⁵R⁶;each of the alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, aryl,benzyl, heteroaryl, heteroalicyclic, alkoxy, alkylthiol,heteroarylthiol, aryloxy, heteroaryloxy or arylthiol of R⁵, R⁶, R⁷, R⁸or R⁹ is optionally substituted with one or more of alkyl, haloalkyl,alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR⁵)₂,trihalomethyl, cyano, S(═O)—R⁵, S(═O)₂—R⁵, S(═O)₂—NR⁵R⁶, halide,cycloalkyl, alkoxy, nitro, NR⁵R⁶, C(O)NR⁵R⁶, N(R⁵)C(═O)—R⁶, hydroxy,alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR⁵, C(═O)—R⁵,aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) or any combinationthereof; and n is an integer between 0 and 10.

FIG. 5 illustrates an improvement in cycling lifetime achieved by aphosphorane-based additive, according to some embodiments of theinvention. Specifically, FIG. 5 illustrates a ca. two-fold increase incycling lifetime using compound 70 listed below, and fast-chargingcycling (6C charging 1C discharging), using two different end of lifecriteria (cell capacity decrease to 80% and 86% of initial capacity).The experiment was performed with an anode load of ca. 2 mg/cm²,NMC-based cathodes with a cathode load of ca. 16 mg/cm², and 3/3.5/3.5VC/EB/BA as baseline electrolyte. Disclosed additives improved cyclinglifetime by ca. 60-90%, depending on the experimental conditions.

Compound 70:

In some embodiments, the electrolytic additives are represented by thestructure of Formula (VI):

WhereinR¹⁰ is H, alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl orheteroaryl;R¹¹-R¹⁴ are each independently H, alkyl, haloalkyl, alkenyl, alkynyl,cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy,O—P(═O)(OR¹⁰)₂, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol,heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR¹⁰R^(10′), NR¹⁰R^(10′), N(R¹⁰)C(═O)—R^(10′), C(═O)—OR¹⁰,S(═O)—R¹⁰, S(═O)₂—R¹⁰ or S(═O)₂—NR¹⁰R^(10′);each of the alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, aryl,benzyl, heteroaryl, heteroalicyclic, alkoxy, alkylthiol,heteroarylthiol, aryloxy, heteroaryloxy or arylthiol of R¹⁰, R¹¹, R¹²,R¹³ or R¹⁴ is optionally substituted with one or more of alkyl,haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR¹⁰2, trihalomethyl, cyano, S(═O)—R¹⁰, S(═O)₂—R¹⁰, S(═O)₂—NR¹⁰R^(10′),halide, cycloalkyl, alkoxy, nitro, NR¹⁰R^(10′), C(O)NR¹⁰R^(10′),N(R¹⁰)C(═O)—R^(10′), hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR¹⁰, C(═O)—R¹⁰, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof;R^(10′) is H, alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic,benzyl or heteroaryl; andn is an integer between 0 and 10.

In some embodiments, the electrolytic additives are represented by thestructure of Formula (VII):

whereinZ³ is OR¹⁵ or NR¹⁵R^(15′) wherein R¹⁵, R^(15′) and the adjacent nitrogenmay form together a heteroaryl or a heteroalicyclic ring;R¹⁵ and R^(15′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl;R¹⁶-R¹⁸ are each independently H, alkyl, haloalkyl, alkenyl, alkynyl,cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy,O—P(═O)(OR¹⁵)₂, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol,heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR¹⁵R^(15′), NR¹⁵R^(15′), N(R¹⁵)C(═O)—R^(15′), C(═O)—OR¹⁵,S(═O)—R¹⁵, S(═O)₂—R¹⁵ or S(═O)₂—NR¹⁵R^(15′);R¹⁶, R¹⁷ and the adjacent carbon may form together a cycloalkyl ring;each of the alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, aryl,benzyl, heteroaryl, heteroalicyclic, heteroaryl or heteroalicyclic ringformed from R¹⁵, R^(15′) and the adjacent nitrogen, cycloalkyl ringformed from R¹⁶, R¹⁷ and the adjacent carbon, alkoxy, alkylthiol,heteroarylthiol, aryloxy, heteroaryloxy, arylthiol of R¹⁵, R^(15′), R¹⁶,R′⁷ or R¹⁸ is optionally substituted with one or more of alkyl,haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(R¹⁵)₂,trihalomethyl, cyano, S(═O)—R¹⁵, S(═O)₂—R¹⁵, S(═O)₂—NR¹⁵R^(15′), halide,cycloalkyl, alkoxy, nitro, NR¹⁵R^(15′), C(O)NR¹⁵R^(15′),N(R¹⁵)C(═O)—R¹⁵, hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol,C(═O)—OR¹⁵, C(═O)—R¹⁵, aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) orany combination thereof; andn is an integer between 0 and 10.

In another embodiment, the electrolytic additives are represented by thestructure of Formula (VIIa):

whereinR¹⁵-R¹⁸ are described hereinabove.

In another embodiment, the electrolytic additives are represented by thestructure of Formula (VIIai):

whereinR¹⁹-R²³ are each independently H, alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl or heteroaryl;R²⁴-R²⁷ are each independently H, alkyl, haloalkyl, alkenyl, alkynyl,cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy,O—P(═O)(OR¹⁵)₂, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol,heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR¹⁵R^(15′), NR¹⁵R^(15′), N(R¹⁵)C(═O)—R^(15′), C(═O)—OR¹⁵,S(═O)—R¹⁵, S(═O)₂—R¹⁵ or S(═O)₂—NR¹⁵R^(15′);each of the alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, aryl,benzyl, heteroaryl, heteroalicyclic, alkoxy, alkylthiol,heteroarylthiol, aryloxy, heteroaryloxy or arylthiol of R¹⁹, R²⁰, R²¹,R²², R²³, R²⁴, R²⁵, R¹²⁶ or R²⁷ is optionally substituted with one ormore of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,O—P(═O)(OR¹⁵)₂, trihalomethyl, cyano, S(═O)—R¹⁵, S(═O)₂—R¹⁵,S(═O)₂—NR¹⁵R^(15′), halide, cycloalkyl, alkoxy, nitro, NR¹⁵R^(15′),C(O)NR¹⁵R^(15′), N(R¹⁵)C(═O)—R^(15′), hydroxy, alkylthiol, thiol,arylthiol, heteroarylthiol, C(═O)—OR¹⁵, C(═O)—R¹⁵, aryl, aryloxy,heteroaryloxy, (CH₂CH₂O)_(n+1) or any combination thereof;R¹⁵ and R^(15′) are described hereinabove; andn is an integer between 0 and 10.

In another embodiment, the electrolytic additives are represented by thestructure of Formula (VIIb):

whereinR¹⁵-R¹⁸ and R^(15′) are described hereinabove.

In another embodiment, the electrolytic additives are represented by thestructure of Formula (VIIbi):

whereinR²⁸-R³² are each independently H, alkyl, haloalkyl, alkenyl, alkynyl,cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy,O—P(═O)(OR¹⁵)₂, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol,heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR¹⁵R^(15′), NR¹⁵R^(15′), N(R¹⁵)C(═O)—R^(15′), C(═O)—OR¹⁵,S(═O)—R¹⁵, S(═O)₂—R¹⁵ or S(═O)₂—NR¹⁵R^(15′);each of the alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, aryl,benzyl, heteroaryl, heteroalicyclic, alkoxy, alkylthiol,heteroarylthiol, aryloxy, heteroaryloxy or arylthiol of R²⁸, R²⁹, R³⁰,R³¹ or R³² is optionally substituted with one or more of alkyl,haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,O—P(═O)(OR¹⁵)₂, trihalomethyl, cyano, S(═O)—R¹⁵, S(═O)₂—R¹⁵,S(═O)₂—NR¹⁵R^(15′), halide, cycloalkyl, alkoxy, nitro, NR¹⁵R^(15′),C(O)NR¹⁵R^(15′), N(R¹⁵)C(═O)—R^(15′), hydroxy, alkylthiol, thiol,arylthiol, heteroarylthiol, C(═O)—OR¹⁵, C(═O)—R¹⁵, aryl, aryloxy,heteroaryloxy, (CH₂CH₂O)_(n+1) or any combination thereof;R¹⁵ and R^(15′) are described hereinabove; andn is an integer between 0 and 10.

In some embodiments, the electrolytic additives are represented by thestructure of Formula (VIII):

whereinR³³ and R^(33′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl, wherein R³³, R^(33′) andthe adjacent nitrogen may form together a heteroaryl or aheteroalicyclic ring;R³⁴ is H, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl,heteroalicyclic heteroaryl, alkoxy, hydroxy, O—P(═O)(OR³³)₂, thiol,alkylthiol, aryloxy, heteroaryloxy, arylthiol, heteroarylthiol, nitro,halide, trihalomethyl, cyano, benzyl, C(O)NR³³R^(33′), NR³³R^(33′),N(R³³)C(═O)—R^(33′), C(═O)—OR³³, S(═O)—R³³, S(═O)₂—R³³ orS(═O)₂—NR³³R^(33′);each of the alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, aryl,benzyl, heteroaryl, heteroalicyclic, heteroaryl or heteroalicyclic ringformed from R³³, R^(33′) and the adjacent nitrogen, alkoxy, alkylthiol,heteroarylthiol, aryloxy, heteroaryloxy or arylthiol of R³³, R^(33′) orR³⁴ is optionally substituted with one or more of alkyl, haloalkyl,alkenyl, alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR³³)₂,trihalomethyl, cyano, S(═O)—R³³, S(═O)₂—R³³, S(═O)₂—NR³³R^(33′), halide,cycloalkyl, alkoxy, nitro, NR³³R^(33′), C(O)NR³³R^(33′),N(R³³)C(═O)—R^(33′), hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR³³, C(═O)—R³³, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof; andn is an integer between 0 and 10.

In another embodiment, the electrolytic additives are represented by thestructure of Formula (Villa):

whereinR³⁴ is described hereinabove.

In another embodiment, the electrolytic additives are represented by thestructure of Formula (VIIIb):

whereinR³⁴ is described hereinabove.

In some embodiments, the electrolytic additives are represented by thestructure of Formula (IX):

whereinR³⁵ and R^(35′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl, wherein R³⁵, R^(35′) andthe adjacent nitrogen may form together a heteroaryl or heteroalicyclicring;R³⁶-R³⁷ are each independently alkyl, haloalkyl, benzyl, aryl,cycloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,CH(P(═O)(OR³⁵)₂)((C═O)OR^(35′)), CH₂C₆H₅, (CH₂)_(n)(CO)NR³⁵R^(35′) or(CH₂)_(n)(COOR³⁵);each of the alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, aryl,heteroaryl or heteroalicyclic ring formed from R³⁵, R^(35′) and theadjacent nitrogen, benzyl, heteroaryl and heteroalicyclic of R³⁵,R^(35′), R³⁶ or R³⁷ is optionally substituted with one or more of alkyl,haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,O—P(═O)(OR³⁵)₂, trihalomethyl, cyano, S(═O)—R³⁵, S(═O)₂—R³⁵,S(═O)₂—NR³⁵R^(35′), halide, cycloalkyl, alkoxy, nitro, NR³⁵R^(35′),C(O)NR³⁵R^(35′), N(R³⁵)C(═O)—R^(35′), hydroxy, alkylthiol, thiol,arylthiol, heteroarylthiol, C(═O)—OR³⁵, C(═O)—R³⁵, aryl, aryloxy,heteroaryloxy, (CH₂CH₂O)_(n+1) or any combination thereof;X″ is an anion; andn is an integer between 0 and 10.

In some embodiments, the electrolytic additives are represented by thestructure of Formula (X):

whereinR³⁸ and R^(38′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl, wherein R³⁸, R^(38′) andthe adjacent nitrogen may form together a heteroaryl or heteroalicyclicring;R³⁹ is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, CH(P(═O)(OR³⁸)₂)((C═O)OR^(38′)), CH₂C₆H₅,(CH₂)_(n)(CO)NR³⁸R^(38′) or (CH₂)_(n)(COOR³⁸);each of the alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, aryl,heteroaryl or heteroalicyclic ring formed from R³⁸, R^(38′) and theadjacent nitrogen, benzyl, heteroaryl and heteroalicyclic of R³⁸,R^(38′) or R³⁹ is optionally substituted with one or more of alkyl,haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,O—P(═O)(OR³⁸)₂, trihalomethyl, cyano, S(═O)—R³⁸, S(═O)₂—R³⁸,S(═O)₂—NR³⁸R^(38′), halide, cycloalkyl, alkoxy, nitro, NR³⁸R^(38′),C(O)NR³⁸R^(38′), N(R³⁸)C(═O)—R^(38′), hydroxy, alkylthiol, thiol,arylthiol, heteroarylthiol, C(═O)—OR³⁸, C(═O)—R³⁸, aryl, aryloxy,heteroaryloxy, (CH₂CH₂O)_(n+1) or any combination thereof; andn is an integer between 0 and 10.

In some embodiments, the electrolytic additives are represented by thestructure of Formula (XI):

whereinR⁴⁰ and R^(40′) are each independently alkyl, haloalkyl, benzyl, aryl,cycloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,CH(P(═O)(OR⁴¹)₂)((C═O)OR⁴¹), CH₂C₆H₅, (CH₂)_(n)(CO)NR⁴¹R^(41′) or(CH₂)_(n)(COOR⁴¹);each of the alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, aryl,benzyl, heteroaryl and heteroalicyclic of R⁴⁰ or R^(40′) is optionallysubstituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, O—P(═O)(OR⁴¹)₂, trihalomethyl, cyano,S(═O)—R⁴¹, S(═O)₂—R⁴¹, S(═O)₂—NR⁴¹R^(41′), halide, cycloalkyl, alkoxy,nitro, NR⁴¹R^(41′) C(O)NR⁴¹R^(41′), N(R⁴¹)C(═O)—R^(41′), hydroxy,alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR⁴¹, C(═O)—R⁴¹,aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) or any combinationthereof;R⁴¹ and R^(41′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl; andn is an integer between 0 and 10.

In some embodiments, the electrolytic additives are represented by thestructure of Formula (XII):

whereinR⁴² and R^(42′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl, wherein R⁴², R^(42′) andthe adjacent nitrogen may form together a heteroaryl or heteroalicyclicring;R⁴³ and R^(43′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl, wherein R⁴³, R^(43′) andthe adjacent nitrogen may form together a heteroaryl or heteroalicyclicring;each of the alkyl, haloalkyl, cycloalkyl, aryl, heteroaryl orheteroalicyclic ring formed from R⁴², R^(42′) and the adjacent nitrogen,heteroaryl or heteroalicyclic ring formed from R⁴³, R^(43′) and theadjacent nitrogen, benzyl, heteroaryl and heteroalicyclic of R⁴²,R^(42′), R⁴³ or R^(43′) is optionally substituted with one or more ofalkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,O—P(═O)(OR⁴²)₂, trihalomethyl, cyano, S(═O)—R⁴², S(═O)₂—R₄₂,S(═O)₂—NR⁴²R^(42′), halide, cycloalkyl, alkoxy, nitro, NR⁴²R^(42′),C(O)NR⁴²R^(42′), N(R₄₂)C(═O)—R^(42′), hydroxy, alkylthiol, thiol,arylthiol, heteroarylthiol, C(═O)—OR⁴², C(═O)—R⁴², aryl, aryloxy,heteroaryloxy, (CH₂CH₂O)_(n+1) or any combination thereof; andn is an integer between 0 and 10.

In another embodiment, the electrolytic additives are represented by thestructure of Formula (XIIa):

whereinR⁴² and R^(42′) are described hereinabove.

In some embodiments, the dithioester, selenothioester and/orthioselenoester compounds as described hereinabove may be added orreplaced by molecules of the Formula (XIII):

wherein:Z⁴ is halide, alkyl, haloalkyl, aryl, alkenyl, alkynyl, cycloalkyl,heteroaryl, heteroalicyclic, hydroxyl, alkoxy, aryloxy, heteroaryloxy,NR⁴⁴R^(44′), P(═O)R⁴⁴R^(44′), benzyl, thiol, arylthiol, alkylthiol,heteroarylthiol, O(CH₂)_(n)C₄H₄S, amino pyridine, imidazole, cyclicamine, piperazine, N(CH₂CH₂)₂N—C(═S)—S—Z⁵, P(═O)(OR⁴⁴)₂, a polymericmoiety or an oligomeric moiety;Z⁵ is alkyl, haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, alkylthiol, S(═O)₂—R⁴⁴, S(═O)—R⁴⁴,S(═O)₂—NR⁴⁴R^(44′), a polymeric moiety, CH(P(═O)(OR⁴⁴)²)((C═O)OR^(44′)),CH₂C₆H₅, (CH₂)_(n)(CO)NR⁴⁴R^(44′). (CH₂)_(n)COOR⁴⁴,(CH₂)_(n)(CO)NH(C₅H₄N), (CH₂)_(n)SR⁴⁴, (CH₂)_(n)S(═O)R⁴⁴,(CH₂)_(n)S(═O)₂R⁴⁴,

an oligomeric moiety or S—C(═S)—Z⁴;R⁴⁴ and R^(44′) are each independently H, alkyl, haloalkyl, cycloalkyl,benzyl, aryl, heteroalicyclic, heteroaryl, polymeric moiety or anoligomeric moiety, wherein if nitrogen (N) is adjacent to R⁴⁴ andR^(44′) then R⁴⁴, R^(44′) and the adjacent nitrogen may form aheteroaryl or a heteroalicyclic ring;each of the alkyl, haloalkyl, aryl, benzyl, alkenyl, alkynyl,cycloalkyl, heteroaryl, heteroalicyclic, alkoxy, aryloxy, heteroaryloxy,polymeric moiety, oligomeric moiety arylthiol, alkylthiol orheteroarylthiol of Z⁴, Z⁵, R⁴⁴ or R^(44′) is optionally substituted withone or more of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic,heteroaryl, O—P(═O)(OR⁴⁴)₂, trihalomethyl, S(═O)—R⁴⁴, C(═S)—O—R⁴⁴,C(═O)—S—R⁴⁴, S(═O)₂—R⁴⁴, S(═O)₂—NR⁴⁴R^(44′), halide, cycloalkyl, alkoxy,nitro, cyano, NR⁴⁴R^(44′), C(O)NR⁴⁴R^(44′), N(R⁴⁴)C(═O)—R^(44′),hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR⁴⁴,C(═O)—R⁴⁴, aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) or anycombination thereof; and n is an integer between 0 and 10.

In certain embodiments, Z⁴ may be alkyl, haloalkyl, aryl, alkenyl,alkynyl, a polymeric moiety having a carbon chain or an oligomericmoiety having a carbon chain.

In certain embodiments, Z⁴ may be heteroaryl, heteroalicyclic, hydroxyl,alkoxy, aryloxy, heteroaryloxy, NR¹R², thiol, arylthiol, alkylthiol,heteroarylthiol, a polymeric moiety with an electron donating group oran oligomeric moiety with an electron donating group.

In certain embodiments, Z⁴ may be NR⁴⁴R⁴⁴.

In certain embodiments, Z⁵ may be alkyl, haloalkyl, benzyl, aryl,cycloalkyl, alkenyl, alkynyl, a polymeric moiety having a carbon chainor an oligomeric moiety having a carbon chain.

In some embodiments, the dithioester, selenothioester and/orthioselenoester compounds as described hereinabove may be added orreplaced by molecules of the Formula (XIV):

whereinR⁴⁵ and R^(45′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl, wherein R⁴⁵, R^(45′) andthe adjacent nitrogen may form together a heteroaryl or heteroalicyclicring;R⁴⁶ and R^(46′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl;R⁴⁷ is H, alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl orheteroaryl;each of the alkyl, haloalkyl, aryl, benzyl, cycloalkyl, heteroaryl,heteroalicyclic, of R⁴⁵, R^(45′), R⁴⁶, R^(46′) or R⁴⁷ is optionallysubstituted with one or more of alkyl, haloalkyl, alkenyl, alkynyl,heteroalicyclic, heteroaryl, O—P(═O)(OR⁴⁵)₂, trihalomethyl, S(═O)—R⁴⁵,C(═S)—O—R⁴⁵, C(═O)—S—R⁴⁵, S(═O)₂—R⁴⁵, S(═O)₂—NR⁴⁵R^(45′), halide,cycloalkyl, alkoxy, nitro, cyano, NR⁴⁵R^(45′), C(O)NR⁴⁵R^(45′),N(R⁴⁵)C(═O)—R^(45′), hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR⁴⁵, C(═O)—R⁴⁵, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof; andn is an integer between 0 and 10.

In some embodiments, the dithioester, selenothioester and/orthioselenoester compounds as described hereinabove may be added orreplaced by molecules of the Formula (XV):

whereinR⁴⁵ and R^(45′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl, wherein R⁴⁵, R^(45′) andthe adjacent nitrogen may form together a heteroaryl or heteroalicyclicring;R⁴⁶ and R^(46′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl;R⁴⁷ and R^(47′) are each independently H, alkyl, haloalkyl, cycloalkyl,aryl, heteroalicyclic, benzyl or heteroaryl;each of the alkyl, haloalkyl, aryl, benzyl, cycloalkyl, heteroaryl,heteroalicyclic, of R⁴⁵, R^(45′), R⁴⁶, R^(46′), R⁴⁷ or R^(47′) isoptionally substituted with one or more of alkyl, haloalkyl, alkenyl,alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR⁴⁵)₂, trihalomethyl,S(═O)—R⁴⁵, C(═S)—O—R⁴⁵, C(═O)—S—R⁴⁵, S(═O)₂—R⁴⁵, S(═O)₂—NR⁴⁵R^(45′),halide, cycloalkyl, alkoxy, nitro, cyano, NR⁴⁵R^(45′), C(O)NR⁴⁵R^(45′),N(R⁴⁵)C(═O)—R^(45′), hydroxy, alkylthiol, thiol, arylthiol,heteroarylthiol, C(═O)—OR⁴⁵, C(═O)—R⁴⁵, aryl, aryloxy, heteroaryloxy,(CH₂CH₂O)_(n+1) or any combination thereof; andn is an integer between 0 and 10.

In some embodiments, the dithioester, selenothioester and/orthioselenoester compounds as described hereinabove may be added orreplaced by molecules of the Formula (XIII), (XIV), (XV) or anycombination thereof, wherein Formula (XIII)-(XV) are describedhereinabove. In another embodiment, the compounds may be added orreplaced by molecules of the Formula (XIV), (XV) or any combinationthereof.

Specific, non-limiting examples include compounds 102-109 presentedbelow.

In another embodiment, the electrolytic additives are represented by thefollowing non limiting examples:

In various embodiments, disclosed additives may comprise any of thefollowing structures and/or variations and substitutions thereof, e.g.,as RAFT structures:

In various embodiments, disclosed additive(s) may be selected orconfigured to capture reactive oxygen species (ROS) such as oxygenradicals, singlet oxygen (¹O₂), hydrogen peroxide (H₂O₂) and/or anyreactive oxygen-containing compounds including them.

In another experimental setting, graphite-based anodes (without siliconor any other metalloid) were used with NMC-based cathodes in coin cells,comparing the same baseline electrolyte that included vinyl carbonate,butyl acetate and ethyl butyrate with electrolyte that includeddisclosed additive 1a. The cycling life periods were measured by runningfive coin cells at 1C (60 minutes) charging and 1C (60 minutes)discharging cycles, and yielded over doubled lifetimes using disclosedadditive 1a (ca. 230% with respect to the baseline).

The concentration of disclosed additives in the electrolyte may rangebetween 0.01vol % and 10vol %, possibly even up to 20vol %. Typicalconcentrations may range between 0.1vol % and 5vol %, possibly between0.5vol % and 2vol %, e.g., around 1vol %±0.5vol %.

Definitions

In some embodiments, Z¹ is halide, alkyl, haloalkyl, aryl, alkenyl,alkynyl, cycloalkyl, heteroaryl, heteroalicyclic, hydroxyl, alkoxy,aryloxy, heteroaryloxy, NR¹R², P(═O)R¹R², benzyl, thiol, arylthiol,alkylthiol, heteroarylthiol, O(CH₂)_(n)C₄H₄S, amino pyridine, imidazole,cyclic amine, piperazine, N(CH₂CH₂)₂N—C(═S)—S—Z², a polymeric moiety oran oligomeric moiety. Each possibility represents a separate embodimentof this invention.

In some embodiments, Z² is alkyl, haloalkyl, benzyl, aryl, cycloalkyl,alkenyl, alkynyl, heteroalicyclic, heteroaryl, a polymeric moiety,CH(P(═O)(OR¹)₂)((C═O)OR²), CH₂C₆H₅, (CH₂)_(n)(CO)NR¹R², (CH₂)_(n)COOR¹,(CH₂)_(n)(CO)NH(C₅H₄N), (CH₂)_(n)SR¹, (CH₂)_(n)S(═O)R¹,(CH₂)_(n)S(═O)₂R¹,

an oligomeric moiety or S—C(═S)—Z¹. Each possibility represents aseparate embodiment of this invention.

In some embodiments, Z³ is OR¹⁵ or NR¹⁵R^(15′) wherein R¹⁵, 10⁵′ and theadjacent nitrogen may form together a heteroaryl or a heteroalicyclicring. Each possibility represents a separate embodiment of thisinvention.

In some embodiments, Z⁴ is halide, alkyl, haloalkyl, aryl, alkenyl,alkynyl, cycloalkyl, heteroaryl, heteroalicyclic, hydroxyl, alkoxy,aryloxy, heteroaryloxy, NR⁴⁴R^(44′), P(═O)R⁴⁴R^(44′), benzyl, thiol,arylthiol, alkylthiol, heteroarylthiol, O(CH₂)_(n)C₄H₄S, amino pyridine,imidazole, cyclic amine, piperazine, N(CH₂CH₂)₂N—C(═S)—S—Z⁵,P(═O)(OR⁴⁴)₂, a polymeric moiety or an oligomeric moiety. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, Z⁵ is alkyl, haloalkyl, benzyl, aryl, cycloalkyl,alkenyl, alkynyl, heteroalicyclic, heteroaryl, alkylthiol, S(═O)₂—R⁴⁴,S(═O)—R⁴⁴, S(═O)₂—NR⁴⁴R^(44′), a polymeric moiety,CH(P(═O)(OR⁴⁴)₂)((C═O)OR^(44′)), CH₂C₆H₅, (CH₂)_(n)(CO)NR⁴⁴R^(44′)(CH₂)_(n)COOR⁴⁴, (CH₂)_(n)(CO)NH(C₅H₄N), (CH₂)_(n)SR⁴⁴,(CH₂)_(n)S(═O)R⁴⁴, (CH₂)_(n)S(═O)₂R⁴⁴,

an oligomeric moiety or S—C(═S)—Z⁴. Each possibility represents aseparate embodiment of this invention.

In some embodiments, le-R² are each independently H, alkyl, haloalkyl,benzyl, cycloalkyl, aryl, heteroalicyclic, heteroaryl, a polymericmoiety or an oligomeric moiety. In certain embodiments, if nitrogen (N)is adjacent to R¹ and R² then R¹, R² and the adjacent nitrogen form aheteroaryl or a heteroalicyclic ring. Each possibility represents aseparate embodiment of this invention.

In some embodiments, R³ and R^(3′) are each independently H, alkyl,haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclicheteroaryl, alkoxy, hydroxy, O—P(═O)(OR¹)₂, thiol, alkylthiol, aryloxy,heteroaryloxy, arylthiol, heteroarylthiol, nitro, halide, trihalomethyl,cyano, benzyl, NR¹R², C(O)NR¹R², N(R¹)C(═O)—R², C(═O)—OR¹, S(═O)—R¹,S(═O)₂—R¹ or —S(═O)₂—NR¹R². Each possibility represents a separateembodiment of this invention.

In some embodiments, R⁴ is H, alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl or heteroaryl. Each possibility represents aseparate embodiment of this invention.

In some embodiments, R⁵-R⁷ are each independently H, alkyl, haloalkyl,cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, R⁸ is H, alkyl, haloalkyl, alkenyl, alkynyl,cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy,O—P(═O)(OR⁵)₂, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol,heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl, C(O)NR⁵R⁶,NR⁵R⁶, N(R⁵)C(═O)—R⁶, C(═O)—OR⁵, S(═O)—R⁵, S(═O)₂—R⁵ or S(═O)₂—NR⁵R⁶.Each possibility represents a separate embodiment of this invention.

In some embodiments, R⁹ is H, alkyl, haloalkyl, alkenyl, alkynyl,cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy,O—P(═O)(OR⁵)₂, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol,heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl, C(O)NR⁵R⁶,NR⁵R⁶, N(R⁵)C(═O)—R⁶, C(═O)—OR⁵, S(═O)—R⁵, S(═O)₂—R⁶ or S(═O)₂—NR⁵R⁶.Each possibility represents a separate embodiment of this invention.

In some embodiments, R¹⁰ is H, alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl or heteroaryl. Each possibility represents aseparate embodiment of this invention.

In some embodiments, R¹¹-R¹⁴ are each independently H, alkyl, haloalkyl,alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy,hydroxy, O—P(═O)(OR¹⁰ 2, thiol, alkylthiol, aryloxy, heteroaryloxy,arylthiol, heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR¹⁰R¹¹¹, NR¹⁰R^(10′), N(R¹⁰)C(═O)—R¹⁰, C(═O)—OR¹⁰, S(═O)—R¹⁰,S(═O)₂—R¹⁰ or S(═O)₂—NR¹⁰R^(10′). Each possibility represents a separateembodiment of this invention.

In some embodiments, R¹⁵ and R^(15′) are each independently H, alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, R¹⁶-R¹⁸ are each independently H, alkyl, haloalkyl,alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy,hydroxy, O—P(═O)(OR¹⁵)₂, thiol, alkylthiol, aryloxy, heteroaryloxy,arylthiol, heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR¹⁵R^(15′), NR¹⁵R^(15′), N(R¹⁵)C(═O)—R^(15′), C(═O)—OR¹⁵,S(═O)—R¹⁵, S(═O)₂—R¹⁵ or S(═O)₂—NR¹⁵R^(15′). In another embodiment, R¹⁶,R¹⁷ and the adjacent carbon may form together a cycloalkyl ring. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, R¹⁹-R²³ are each independently H, alkyl, haloalkyl,cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, R²⁴-R²⁷ are each independently H, alkyl, haloalkyl,alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy,hydroxy, O—P(═O)(OR¹⁵)₂, thiol, alkylthiol, aryloxy, heteroaryloxy,arylthiol, heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR¹⁵R^(15′), NR¹⁵R^(15′), N(R¹⁵)C(═O)—R^(15′), C(═O)—OR¹⁵,S(═O)—R¹⁵, S(═O)₂—R¹⁵ or S(═O)₂—NR¹⁵R^(15′). Each possibility representsa separate embodiment of this invention.

In some embodiments, R²⁸-R³² are each independently H, alkyl, haloalkyl,alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy,hydroxy, O—P(═O)(OR¹⁵)₂, thiol, alkylthiol, aryloxy, heteroaryloxy,arylthiol, heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR¹⁵R^(15′), NR¹⁵R^(15′), N(R¹⁵)C(═O)—R^(15′), C(═O)—OR¹⁵,S(═O)—R¹⁵, S(═O)₂-R¹⁵ or S(═O)₂—NR¹⁵R^(15′). Each possibility representsa separate embodiment of this invention.

In some embodiments, R³³ and R^(33′) are each independently H, alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl,wherein R³³, R^(33′) and the adjacent nitrogen may form together aheteroaryl or a heteroalicyclic ring. Each possibility represents aseparate embodiment of this invention.

In some embodiments, R³⁴ is H, alkyl, haloalkyl, alkenyl, alkynyl,cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy,O—P(═O)(OR³³)₂, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol,heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR³³R^(33′), NR³³R^(33′), N(R³³)C(═O)—R^(33′), C(═O)—OR³³,S(═O)—R³³, S(═O)₂—R³³ or S(═O)₂—NR³³R^(33′). Each possibility representsa separate embodiment of this invention.

In some embodiments, R³⁵ and R^(35′) are each independently H, alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl,wherein R³⁵, R^(35′) and the adjacent nitrogen may form together aheteroaryl or heteroalicyclic ring. Each possibility represents aseparate embodiment of this invention.

In some embodiments, R³⁶-R³⁷ are each independently alkyl, haloalkyl,benzyl, aryl, cycloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,CH(P(═O)(OR³⁵)₂)((C═O)OR^(35′)), CH₂C₆H₅, (CH₂)_(n)(CO)NR³⁵R³⁵ or(CH₂)_(n)(COOR³⁵). Each possibility represents a separate embodiment ofthis invention.

In some embodiments, R³⁸ and R^(38′) are each independently H, alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl,wherein R³⁸, R^(38′) and the adjacent nitrogen may form together aheteroaryl or heteroalicyclic ring. Each possibility represents aseparate embodiment of this invention.

In some embodiments, R³⁹ is alkyl, haloalkyl, benzyl, aryl, cycloalkyl,alkenyl, alkynyl, heteroalicyclic, heteroaryl,CH(P(═O)(OR³⁸)₂)((C═O)OR^(38′)), CH₂C₆H₅, (CH₂)_(n)(CO)NR³⁸R^(38′) or(CH₂)_(n)(COOR³⁸). Each possibility represents a separate embodiment ofthis invention.

In some embodiments, R⁴⁰ and R^(40′) are each independently alkyl,haloalkyl, benzyl, aryl, cycloalkyl, alkenyl, alkynyl, heteroalicyclic,heteroaryl, CH(P(═O)(OR¹¹)₂)((C═O)OR⁴¹), CH₂C₆H₅,(CH₂)_(n)(CO)NR⁴¹R^(41′) or (CH₂)_(n)(COOR⁴¹). Each possibilityrepresents a separate embodiment of this invention.

In some embodiments, R⁴¹ and R^(41′) are each independently H, alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, R⁴² and R^(42′) are each independently H, alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl,wherein R⁴², R^(42′) and the adjacent nitrogen may form together aheteroaryl or heteroalicyclic ring. Each possibility represents aseparate embodiment of this invention.

In some embodiments, R⁴³ and R^(43′) are each independently H, alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl,wherein R⁴³, R^(43′) and the adjacent nitrogen may form together aheteroaryl or heteroalicyclic ring. Each possibility represents aseparate embodiment of this invention.

In some embodiments, R⁴⁴ and R^(44′) are each independently H, alkyl,haloalkyl, cycloalkyl, benzyl, aryl, heteroalicyclic, heteroaryl,polymeric moiety or an oligomeric moiety, wherein if nitrogen (N) isadjacent to R⁴⁴ and R^(44′) then R⁴⁴, R^(44′) and the adjacent nitrogenmay form a heteroaryl or a heteroalicyclic ring. Each possibilityrepresents a separate embodiment of this invention.

In some embodiments, R⁴⁵ and R^(45′) are each independently H, alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl,wherein R⁴⁵, R^(45′) and the adjacent nitrogen may form together aheteroaryl or heteroalicyclic ring. Each possibility represents aseparate embodiment of this invention.

In some embodiments, R⁴⁶ and R^(46′) are each independently H, alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, R⁴⁷ and R^(47′) are each independently H, alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, R⁴⁸ and R⁴⁹ are each independently alkyl,haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl or heteroaryl. Inanother embodiment, R⁴⁵ is a C₃-C₁₀ alkyl, C₃-C₂₀ alkyl or C₃-C₃₀ alkyl.In another embodiment, R⁴⁶ is a C₄-C₁₀ alkyl, C₄-C₂₀ alkyl or C₄-C₃₀alkyl. Each possibility represents a separate embodiment of thisinvention.

In some embodiments, R^(48′) is a C₃-C₁₀ alkyl, C₃-C₂₀ alkyl or C₃-C₃₀alkyl. Each possibility represents a separate embodiment of thisinvention.

In some embodiments, R^(49′) is C₄-C₁₀ alkyl, C₄-C₂₀ alkyl or C₄-C₃₀alkyl. Each possibility represents a separate embodiment of thisinvention.

In some embodiments, R⁵⁰ and R⁵¹ are each independently H, alkyl,haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroalicyclicheteroaryl, alkoxy, hydroxy, O—P(═O)(OR⁵⁰)₂, thiol, alkylthiol, aryloxy,heteroaryloxy, arylthiol, heteroarylthiol, nitro, halide, trihalomethyl,cyano, benzyl, C(O)NR⁵⁰R⁵¹, NR⁵⁰R⁵¹, N(R⁵⁰)C(═O)—R⁵¹, C(═O)—OR⁵⁰,S(═O)—R⁵⁰, S(═O)₂—R⁵⁰ or S(═O)₂—NR⁵⁰R⁵¹. Each possibility represents aseparate embodiment of this invention.

In some embodiments, M¹ is a metal selected from Si, Ti, Zr and Al. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, n is an integer between 0 and 10. In oneembodiment, n is an integer between 0-2, 2-5 or 5-10. Each possibilityrepresents a separate embodiment of this invention.

In some embodiments, p is an integer between 1 and 1000. In oneembodiment, p is an integer between 1-100, 100-200, 200-300, 300-400,400-500, 500-600, 600-700, 700-800, 800-900 or 900-1000. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, n is an integer between 0 and 10. one embodiment,n³ is 1. In one embodiment, n is 2. In one embodiment, n is 3. In oneembodiment, n is 4. In one embodiment, n is 5. In one embodiment, n is6. In one embodiment, n is 7. In one embodiment, n is 8. In oneembodiment, n is 9. In one embodiment, n is 10. Each possibilityrepresents a separate embodiment of this invention.

In some embodiments, n¹ is an integer between 1 and 3. In oneembodiment, when M¹ is Si, Ti or Zr, n¹ is an integer between 1 and 3.In one embodiment, when M¹ is Al, n¹ is an integer between 1 and 2. Eachpossibility represents a separate embodiment of this invention.

In some embodiment, n² is 3 or 4. In one embodiment, when M¹ is Si, Tior Zr, n² is 4. In one embodiment, when M¹ is Al, n² is 3. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, n³ is an integer between 0 and 10. In oneembodiment, n³ is 0. In one embodiment, n³ is 1. In one embodiment, n³is 2. In one embodiment, n³ is 3. In one embodiment, n³ is 4. In oneembodiment, n³ is 5. In one embodiment, n³ is 6. In one embodiment, n³is 7. In one embodiment, n³ is 8. In one embodiment, n³ is 9. In oneembodiment, n³ is 10. Each possibility represents a separate embodimentof this invention.

In some embodiments, L is a linker which is at least one of: a polymericmoiety, an oligomeric moiety, a functional group or any combinationthereof where the polymeric moiety, oligomeric moiety and the functionalgroup are as defined herein below. Each possibility represents aseparate embodiment of this invention.

In some embodiments, the core is a dendritic, oligomeric or polymericmoiety, where the dendritic moiety, oligomeric moiety and polymericmoiety are as defined herein below. Each possibility represents aseparate embodiment of this invention.

In some embodiments, X″ is an anion. In another embodiment, the anion isa monovalent. In another embodiment the anion is polyvalent. In someembodiments, X″ is a triflate (CF₃SO₃ ⁻).

In another embodiment the anion is sulfate, dodecylsulfate (SDS),chloride, bromide, iodide, perchlorate, nitrate, trifluoroacetate,hydroxide, hydrosulfide, sulfide, nitrite, carboxylate, dicarboxylate,sulfonate, tetraflouroborate hexaflourophosphate, hexafluoroarsenate([AsF₆]⁻), hexafluoroantimonate ([SbF₆]⁻), hypophosphite, phosphate,phosphite, cyanate, cyanide, isocyanate, thiocyanate, tetracyanoborate([B(CN)_(4]) ⁻), tricyanomethanide ([(NC)₃C]⁻), dicyanamide ([(NC)₂N]⁻),triarylmethanide ([(Aryl)₃C]⁻) wherein aryl is as defined hereinabove,tetralkylborate, tetraarylborate, Difluoro(oxalato)borate,tetrahydroxyborate, bis(oxalato)borate, chromate or sulfonylimide. Inanother embodiment, non-limiting groups of the carboxylate includeformate, propionate, butyrate, lactate, pyruvate, tartrate, ascorbate,gluconate, glutamate, citrate, succinate, maleate,4-pyridinecarboxylate, 2-hydroxypropanoate, oleate and glucoronate. Inanother embodiment, non-limiting groups of the sulfonate includemesylate, tosylate, ethanesulfonate, benzenesulfonate, dioctylsulfosuccinate and triflate. In another embodiment, non-limiting groupsof the tetraalkylborates include tetramethylborate, trimethylethylborateand triethylbutylborate. In another embodiment, non-limiting groups ofthe tetraaryylborates include tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tetrakis(4-chlorophenyl)borate,tetrakis(pentafluorophenyl)borate and tetrakis(4-fluorophenyl)borate. Inanother embodiment, the term “sulfonylimide” refers to any anion of thestructure {[Ewg-SO₂]₂N}⁻, where “Ewg” is an electron withdrawing moiety.In another embodiment, non-limiting examples of the Ewg include: halideas defined hereinabove, nitro (NO₂), cyano (CN) and haloalkyl as definedhereinabove. In another embodiment, non-limiting examples of thesulfonylimide include: bis(trifluoromethane)sulfonimide (TFSI),bis(fluoro sulfonyl)imide (FSI) and bis(pentafluoroethyl sulfonyl)imide(BETI). In another embodiment, non-limiting examples of thetriarylmethanide include: triphenylmethanide andtris(nitrophenyl)methanide.

In some embodiments, the term “alkyl” comprises an aliphatic hydrocarbonincluding straight chain and branched chain groups. Preferably, thealkyl group has 1 to 100 carbon atoms, 1-10 carbon atoms, 3-10 carbonatoms, 4-10 carbon atoms, 10-20 carbon atoms, 3-20 carbon atoms, 4-20carbon atoms, 20-30 carbon atoms, 3-30 carbon atoms, 4-30 carbon atoms,30-40 carbon atoms, 40-50 carbon atoms, 50-60 carbon atoms, 60-70 carbonatoms, 70-80 carbon atoms, 80-90 carbon atoms or 90-100 carbon atoms.Whenever a numerical range; e.g., “1-100”, is stated herein, it impliesthat the group, in this case the alkyl group, may contain 1 carbon atom,2 carbon atoms, 3 carbon atoms, etc., up to and including 100 carbonatoms. In certain embodiments, an alkyl group may be substituted orunsubstituted by one or more substituents. Each possibility represents aseparate embodiment of this invention.

In some embodiments, the term “alkenyl” refers to an unsaturated alkyl,as defined herein, having at least two carbon atoms and at least onecarbon-carbon double bond. In certain embodiments, an alkenyl group maybe substituted or unsubstituted by one or more substituents. Eachpossibility represents a separate embodiment of this invention.

In some embodiments, the term “alkynyl” refers to an unsaturated alkylhaving at least two carbon atoms and at least one carbon-carbon triplebond. In certain embodiments, an alkynyl group may be substituted orunsubstituted by one or more substituents. Each possibility represents aseparate embodiment of this invention.

In some embodiments, the term “cycloalkyl” refers to an all-carbonmonocyclic or fused ring (e.g., rings which share an adjacent pair ofcarbon atoms) group where one or more of the rings does not have acompletely conjugated pi-electron system. In certain embodiments, acycloalkyl group may be substituted or unsubstituted by one or moresubstituents. Each possibility represents a separate embodiment of thisinvention.

In some embodiments, the term “aryl” refers to an all-carbon monocyclicor fused-ring polycyclic (e.g., rings which share adjacent pairs ofcarbon atoms) groups having a completely conjugated pi-electron system.In certain embodiments, an aryl group may be substituted orunsubstituted by one or more substituents. Each possibility represents aseparate embodiment of this invention.

In some embodiments, the term “heteroaryl” refers to a monocyclic orfused ring (e.g., rings which share an adjacent pair of atoms) grouphaving in the ring(s) one or more atoms, such as, for example, nitrogen,oxygen and sulfur and, in addition, having a completely conjugatedpi-electron system. Examples, without limitation, of heteroaryl groupsinclude succinimide, pyrrole (e.g. 1H-pyrrole or 2H-pyrrole), indole,furan, thiophene, thiadiazole, imidazole, oxazole, thiazole, pyrazole,pyridine, pyrimidine, pyrrolidone (e.g. 2-pyrrolidone or 3-pyrrolidone),quinoline, isoquinoline and purine. The heteroaryl group may besubstituted or unsubstituted by one or more substituents. Eachpossibility represents a separate embodiment of this invention.

In some embodiment, the term “heteroalicyclic” or “heterocyclyl” refersto a monocyclic or fused ring group having in the ring(s) one or moreatoms such as nitrogen, oxygen and/or sulfur. The rings may also haveone or more double bonds. In certain embodiments, the rings do not havea completely conjugated pi-electron system. Examples, withoutlimitation, include: piperidine, piperazine, tetrahydrofuran,tetrahydropyran, morpholine and the like. The heteroalicyclic orheterocyclyl group may be substituted or unsubstituted by one or moresubstituents. Each possibility represents a separate embodiment of thisinvention.

In some embodiments, the term “polymeric moiety” refers to a moietycomprising a polymeric chain and optionally one or more functionalgroups, defined hereinbelow, linked to the polymeric chain. In someembodiments, the polymeric chain is substituted or unsubstituted by oneor more substituents. In some embodiments, the polymeric moiety is alinker or a part of a linker, i.e. it's connected from both sides of themoiety (see polyethylene glycol (PEG) examples below for illustration).In some embodiments, the polymeric moiety is connected from only oneside (see polyethylene glycol (PEG) examples below for illustration). Insome embodiments, non-limiting examples of polymers include:polyethylene glycol (PEG), polyacrylic acid (PAA), polysaccharides,polypeptides, polynucleotides, polyalkylamines and poly silanes. In someembodiments, non-limiting examples of polysaccharides include:cellulose, starch, glycogen, chitin, amylose and amylopectin. In someembodiments, non-limiting examples of polypeptides include polylysine,polyarginine, polyglycine, polyalanine, cathelicidins, eledoisin andcalcitonin. In some embodiments, non-limiting examples ofpolynucleotides include: RNA and DNA. In some embodiments, non-limitingexamples of polyalkylamines include linear and branched polyethyleneimines. In some embodiments, non-limiting examples of polysilanesinclude polydimethylsiloxane (PDMS) and polymethylhydrosiloxane. Eachpossibility represents a separate embodiment of this invention. In someembodiments, the polymer is a homopolymer or copolymer of the polymersas described hereinabove. In some embodiments, the number of repeatingunits in one polymeric chain is above 5. In some embodiments, the numberof repeating units is 6-10. In some embodiments, the number of repeatingunits is 10-20. In some embodiments, the number of repeating units is20-50. In some embodiments, the number of repeating units is 50-100. Insome embodiments, the number of repeating units is 100-500. In someembodiments, the number of repeating units is 500-1,000. In someembodiments, the number of repeating units is 1,000-5,000. In someembodiments, the number of repeating units is 5,000-10,000. In someembodiments, the number of repeating units is 10,000-50,000. In someembodiments, the number of repeating units is 50,000-100,000. In someembodiments, the number of repeating units is 100,000-500,000. Eachpossibility represents a separate embodiment of this invention. In someembodiments, the polymeric moiety is

where q is an integer between 6 and 10,000. In some embodiments, thepolymeric moiety is

where q is an integer between 6 and 10,000.

In some embodiments, non-limiting examples of functional groups include—O— (ether), —S— (thioether), —O—C(═O)— (ester), —S—C(═S)—(dithioester), —NR¹— (amine), —NR¹C(═O)— (amide), —(CR¹R²)_(n)—(alkylene), —(C(halide)₂)_(n+1)-(haloalkylene), —S(═O)—(sulfoxide),—S(═O)₂— (sulfone), substituted or unsubstituted arylene, substituted orunsubstituted heteroarylene, substituted or unsubstituted cycloalkyleneand substituted or unsubstituted heterocyclylene where n is an integerbetween 0 and 10, R¹ and R² are as defined hereinabove and arylene,heteroarylene, cycloalkylene and heterocyclylene correspond to thehereinabove definitions of aryl, heteroaryl, cycloalkyl andheterocyclyl, respectively. Each possibility represents a separateembodiment of this invention.

In some embodiments, the term “oligomeric moiety” refers to a moietycomprising an oligomeric chain and optionally one or more functionalgroups, defined hereinabove, linked to the oligomeric chain. In someembodiments, the oligomeric moiety is substituted or unsubstituted byone or more substituents. In some embodiments, the oligomeric moiety isa linker or a part of a linker, i.e. it's connected from both sides ofthe moiety (see oligoethylene glycol examples below for illustration).In some embodiments, the oligomeric moiety is connected from only oneside (see oligoethylene glycol examples below for illustration). In someembodiments, non-limiting examples of oligomers include the samemonomers of the polymers as described hereinabove, i.e. ethylene glycol(EG), acrylic acid (PAA), saccharides, peptides, nucleotides,alkylamines and silanes, where the number of repeating units in oneoligomeric chain is 2-5. Each possibility represents a separateembodiment of this invention. In some embodiments, the oligomeric moietyis

where r is an integer between 2 and 5. In some embodiments, theoligomeric moiety is

where r is an integer between 2 and 5.

In some embodiments, a dendritic core or a dendrimeric moiety, isdefined as repetitively branched molecular moiety. In some embodiments,the dendritic moiety has an atom center (e.g. carbon atom) or amolecular center (e.g. adamantane), where such center is multiplysubstituted with branches (or “arms”) such as functionalized (e.g. withesters or ethers) alkyls and each of these branches is further multiplysubstituted with identical/other branches; this multiplesubstitution/functionalization occurs at least once in the smallestdendritic moiety (i.e. carbon with 4 arms) and may occur more than once,when each such substitution/functionalization is referred to as“generation” (i.e. one functionalization of e.g. carbon, the initiator,resulting in tetra-functionalized methane is a zero generation;subsequent full functionalization of all these four branches withadditional branches will result in 12 branches as the first generationand so on). Each possibility represents a separate embodiment of thisinvention.

In some embodiments, the term “alkoxy” refers to —O-alkyl or an—O-cycloalkyl group and the term “alkylthiol” describes an —S-alkyl oran —S-cycloalkyl group, where alkyl and cycloalkyl are as definedhereinabove. In certain embodiments, the term “aryloxy” and“heteroaryloxy” describe an —O-aryl and an —O-heteroaryl groups,respectively and the term “arylthiol” and “heteroarylthiol” describe an—S-aryl and an —S—heteroaryl groups, where aryl and heteroaryl are asdefined hereinabove.

In some embodiments, “halide”, “halogen” or “halo” refer to fluorine,chlorine, bromine or iodine.

In some embodiments, the term “haloalkyl” refers to alkyl substitutedwith at least one halide where alkyl and halide are as definedhereinabove. The haloalkyl group may be substituted or unsubstituted byone or more substituents other than halides. Non-limiting examples ofhaloalkyl include CF₃, CF₂CF₃, CH₂CF₃, CCl₃, CCl₂CCl₃, CH₂CCl₃,CH₂CH₂CF₃. CH₂CF₂CF₃ and CF₂CF₂CF₃. Each possibility represents aseparate embodiment of this invention.

In some embodiments, the term “hydroxy” refers to —OH group and the term“thiol” describes a —SH group.

In some embodiments, the term “nitro” group refers to a —NO₂ group.

In some embodiments, the term “cyano” or “nitrile” group refers to a—C≡N group.

In some embodiments, non-limiting examples for substituents include:alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,O—P(═O)(OR′)₂ or O—P(═O)(OR⁵)₂ or O—P(═O)(OR¹⁰)₂ or O—P(═O)(OR¹⁵)₂ orO—P(═O)(OR³³)₂ or O—P(═O)(OR³⁵)₂ or O—P(═O)(OR³⁸)₂ or O—P(═O)(OR⁴¹)₂ orO—P(═O)(OR⁴²)₂ or O—P(═O)(OR⁴⁴)₂ or O—P(═O)(OR⁴⁵)₂ or O—P(═O)(OR⁴⁶)₂ orO—P(═O)(OR⁴⁷)₂ or O—P(═O)(OR⁴⁸)₂ or O—P(═O)(OR⁵⁰), trihalomethyl,S(═O)—R¹ or S(═O)—R⁵ or S(═O)—R¹⁰ or S(═O)—R¹⁵ or S(═O)—R³³ or S(═O)—R³⁵or S(═O)—R³⁸ or S(═O)—R⁴¹ or S(═O)—R⁴² or S(═O)—R⁴⁴ or S(═O)—R⁴⁵ orS(═O)—R⁴⁶ or S(═O)—R⁴⁷ or S(═O)—R⁴⁸ or S(═O)—R⁵⁰, S(═O)₂—R¹ or S(═O)₂—R⁵or S(═O)₂—R¹⁰ or S(═O)₂—R¹⁵ or S(═O)₂—R³³ or S(═O)₂—R³⁵ or S(═O)₂—R³⁸ orS(═O)₂—R⁴¹ or S(═O)₂—R⁴² or S(═O)₂—R⁴⁴ or S(═O)₂—R⁴⁵ or S(═O)₂—R⁴⁶ orS(═O)₂—R⁴⁷ or S(═O)₂—R⁴⁸ or S(═O)₂—R⁵⁰, S(═O)₂—NR¹R² or S(═O)₂—NR⁵R⁶ orS(═O)₂—NR¹⁰R^(10′) or S(═O)₂—NR¹⁵R^(15′) or S(═O)₂—NR³³R^(33′) orS(═O)₂—NR³⁵R^(35′) or S(═O)₂—NR³⁸R^(38′) or S(═O)₂—NR⁴¹R^(41′) orS(═O)₂—NR⁴²R^(42′) or S(═O)₂—NR⁴⁴R^(44′) or S(═O)₂—NR⁴⁵R^(45′) orS(═O)₂—NR⁴⁶R^(46′) or S(═O)₂—NR⁴⁷R^(47′) or S(═O)₂—NR⁴⁸R⁴⁹ orS(═O)₂—NR⁵⁰R⁵¹, halide, cycloalkyl, alkoxy, nitro, NR¹R² or NR⁵R⁶ orNR¹⁰R^(10′) or NR¹⁵R^(15′) or NR³³R^(33′) or NR³⁵R^(35′) or NR³⁸R^(38′)or NR⁴¹NR^(41′) or NR⁴²R^(42′) or NR⁴⁴R^(44′) or NR⁴⁵R^(45′) orNR⁴⁶R^(46′) or NR⁴⁷R⁴⁷ or NR⁴⁸R⁴⁹ or NR⁵⁰R⁵¹, C(O)NR¹R² or C(O)NR⁵R⁶ orC(O)NR¹⁰R^(10′) or C(O)NR¹⁵R^(15′) or C(O)NR³³R^(33′) or C(O)NR³⁵R^(35′)or C(O)NR³⁸R^(38′) or C(O)NR⁴¹R^(41′) or C(O)NR⁴²R^(42′) orC(O)NR⁴⁴R^(44′) or C(O)NR⁴⁵R^(45′) or C(O)NR⁴⁶R^(46′) or C(O)NR⁴⁷R^(47′)or C(O)NR⁴⁸R⁴⁹ or C(O)NR⁵⁰R⁵¹, N(R¹)C(═O)—R² or NR⁵C(═O)R⁶ orNR¹⁰C(═O)R^(10′) or NR¹⁵C(═O)R^(15′) or NR³³C(═O)R^(33′) orNR³⁵C(═O)R^(35′) or NR³⁸C(═O)R^(38′) or NR⁴¹C(═O)R^(41′) orNR⁴²C(═O)R^(42′) or NR⁴⁴C(═O)R^(44′) or NR⁴⁵C(═O)R^(45′) orNR⁴⁶C(═O)R^(46′) or NR⁴⁷C(═O)R^(47′) or NR⁴⁸C(═O)R⁴⁹ or NR⁵⁰C(═O)R⁵¹,hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR¹ orC(═O)—OR⁵ or C(═O)—OR¹⁰ or C(═O)—OR¹⁵ or C(═O)—OR³³ or C(═O)—OR³⁵ orC(═O)—OR³⁸ or C(═O)—OR⁴¹ or C(═O)—OR⁴² or C(═O)—OR⁴⁴ or C(═O)—OR⁴⁵ orC(═O)—OR⁴⁶, or C(═O)—OR⁴⁷, or C(═O)—OR⁴⁸, or C(═O)—OR⁵⁰, C(═O)—R¹ orC(═O)—R⁵ or C(═O)—R¹⁰ or C(═O)—R¹⁵ or C(═O)—R³³ or C(═O)—R³⁵ orC(═O)—R³⁸ or C(═O)—R⁴¹ or C(═O)—R⁴² or C(═O)—R⁴⁴ or C(═O)—R⁴⁵ orC(═O)—R⁴⁶ or C(═O)—R⁴⁷ or C(═O)—R⁴⁸ or C(═O)—R⁵⁰, aryl, aryloxy,heteroaryloxy, C(═S)—O—R¹ or C(═S)—O—R⁵ or C(═S)—O—R¹⁰ or C(═S)—O—R¹⁵ orC(═S)—O—R³³ or C(═S)—O—R³⁵ or C(═S)—O—R³⁸ or C(═S)—O—R⁴¹ or C(═S)—O—R⁴²or C(═S)—O—R⁴⁴ or C(═S)—O—R⁴⁵ or C(═S)—O—R⁴⁶ or C(═S)—O—R⁴⁷ orC(═S)—O—R⁴⁸ or C(═S)—O—R⁵⁰, C(═O)—S—R¹ or C(═O)—S—R⁵ or C(═O)—S—R¹⁰ orC(═O)—S—R¹⁵ or C(═O)—S—R³³ or C(═O)—S—R³⁵ or C(═O)—S—R³⁸ or C(═O)—S—R⁴¹or C(═O)—S—R⁴² or C(═O)—S—R⁴⁴ or C(═O)—S—R⁴⁵ or C(═O)—S—R⁴⁶ orC(═O)—S—R⁴⁷ or C(═O)—S—R⁴⁸ or C(═O)—S—R⁵⁰, (CH₂CH₂O)_(n+1), or anycombination thereof. Each possibility represents a separate embodimentof this invention.

Electrolyte additives as described hereinabove are provided, whichimprove the formation and operation of lithium ion battery, inparticular fast-charging lithium-ion batteries having anodes with anodematerial which is based on any of Si, Ge and/or Sn. In some embodiments,the disclosed additives increase the cycling lifetime of the batteries,which is a critical parameter of their performance.

In certain embodiments, VC or poly-VC may be added to the anode slurryand/or to the binder, to reduce electrolyte consumption and to improvecontrol of the poly-VC chain lengths. Poly-VC may build an artificialSEI on the anode material particles even before, or during formation. Insuch embodiments, the electrolyte may have less VC (e.g., 5%, 10%, 20%),to reduce its viscosity. Poly-VC for the anode slurry (or binder) may beprepared with polymerization controlling agent to control the molecularweights of the chains (chain length). Electrolyte modifications andanode modifications may be combined and optimized.

In certain embodiments, sacrificial lithium salts may be used in theelectrolyte during the formation stage, and/or as part of the anodeslurry and/or the cathode formulation—to compensate for lithium lossesduring the formation stage (e.g., caused by SEI formation) and toincrease the energy density. Disclosed lithium salts may enhance lithiumcontent in the electrolyte and/or in the anode and/or in the cathode(e.g., having higher lithium density than respective cathode materials),and possibly be removed as gaseous compounds such as N₂, CO₂, CO, COS,etc. at a degassing stage after cell formation cycles. Advantageously,removal of the supporting molecular structure (that binds the lithium inthe salt) by degassing reduces the volume of non-active material in thecell.

Suggested sacrificial lithium salts include any of the following,substituted or un-substituted, as well as derived compounds: Lithiumazodicarboxylate, Lithium bicarbonate R—C(═S)SLi, R—C(═O)SLi, R—C(═S)OLiand Lithium sulfinates, R—SO₂Li, where R is e.g., alkyl, haloalkyl,cycloalkyl, carbonyl (e.g., formyl CHO, alkyl or aryl carbonyls withvarious residues), thiocarbonyl (e.g., thioformyl CHS, alkyl or arylthiocarbonyls with various residues), aryl, NR¹R², thiol, arylthiol,alkylthiol, heteroarylthiol, heteroalicyclic or heteroaryl; and wherealkyl, haloalkyl, cycloalkyl, caroyl, thiocarboyl, aryl, NR¹R², thiol,arylthiol, alkylthiol, heteroarylthiol, heteroalicyclic or heteroarylare defined hereinabove.

Non-limiting examples for sacrificial lithium salts include:

In certain embodiments, any one or more of the oxygen atoms may beexchanged by a sulfur atom.

Non-limiting examples for Lithium azodicarboxylate and Lithiumbicarbonate include, respectively:

In certain embodiments, Li-poly-aspartate (PAsp) may be used instead of,or in addition to, Li-polyacrylate (PAAc) as binder—for Ge, Si, Sn andpossibly graphite anode materials. PAsp is advantageous in that it isenvironmentally friendly, and possibly improves performance with respectto PAA.

Piezoelectric binders may be used to improve the accommodation of theexpanding active material particle within the binder. Optionally,piezoelectric binders may be selected to expand mechanically at voltagescorresponding to the lithiation voltage of the anode material particles.

Alternatively or complementarily, piezoelectric binders may be selectedso that the mechanical pressure applied by the expanding anode materialparticle on the binder reduces the anode voltage allowingextra-charging.

Combinations of the ideas disclosed above may be modified and optimizedto improve the operation and/or performance of lithium ion batterieswith respect to any of their cycle life, charging/discharging rates,safety and/or capacity.

Any of the disclosed embodiments may be implemented in lithium ionbatteries to improve their cycle life, charging/discharging rates,safety and/or capacity. Lithium ion batteries typically comprise anodesand cathodes with current collectors affixed thereto, packed withelectrolyte and separator(s) in a soft or/and hard package (e.g.,pouches, prismatic or cylindrical packages, etc. Anodes are typicallymade of anode material particles and additional materials, such asconductive additive(s), binder(s), surfactants, dispersive materials,porosity control materials, etc., and may comprise any of the anodeconfigurations taught, e.g., by U.S. Patent Publication No.2017/0294687, incorporated herein by reference in its entirety. Incertain embodiments, polymerization of coating 105 and/or of coatings ofthe anode material particles may be controlled, as disclosed, e.g., inany of U.S. Patent Publication No. 2019/0198912 and U.S. PatentApplication Nos. 62/711,639 and 62/804,778, incorporated herein byreference in their entirety. For example, anodes may be based on carbon(e.g., graphite, graphene or other carbon-based materials), metalloidanode material such as Si, Ge, Sn and their combinations and/or metalssuch as Li-metal. Cathodes may comprise lithium metal oxide (LiMeO),wherein Me can be one or several metals selected from Ni, Co, Fe, Mn andAl or sulfur-based cathodes. For example, cathodes may comprisematerials based on layered, spinel and/or olivine frameworks, such asLCO formulations (based on LiCoO₂), NMC formulations (based on lithiumnickel-manganese-cobalt), NCA formulations (based on lithium nickelcobalt aluminum oxides), LMO formulations (based on LiMn₂O₄), LMNformulations (based on lithium manganese-nickel oxides) lithiumiron-phosphorus oxide (LFP) formulations (based on LiFePO₄), lithiumrich cathodes, and/or combinations thereof. Cathodes may furthercomprise additive (e.g., conductive additives), binders, etc.Separator(s) may comprise various materials, e.g., polymers such as anyof polyethylene (PE), polypropylene (PP), polyethylene terephthalate(PET), poly vinylidene fluoride (PVDF), polymer membranes such as apolyolefin, polypropylene, or polyethylene membranes. Multi-membranesmade of these materials, micro-porous films and/or spray coatingthereof, woven or non-woven fabrics etc. may be used as separator(s), aswell as possibly composite materials including, e.g., alumina, zirconia,titania, magnesia, silica and calcium carbonate along with variouspolymer components as listed above.

In any of the disclosed embodiments, electrolytes may be based on liquidelectrolytes, typically linear and cyclic carbonates andmonothiocarbonates, such as EC (ethylene carbonate), DC (diethylcarbonate), PC (propylene carbonate), VC (vinylene carbonate), FEC(fluoroethylene carbonate), DEC (diethyl carbonate), EB (ethylbutyrate), BA (butyl acetate), EA (ethyl acetate), EMC (ethyl methylcarbonate), DMC (dimethyl carbonate), 1,3-dioxole-2-thione andcombinations thereof.

In various embodiments, the electrolytes may comprise any liquid,polymer, gel (e.g., inorganic silica gel electrolytes), glass (e.g.,amorphous sulfides-based electrolytes), solid polymer electrolytes(e.g., polyethylene oxide, fluorine-containing polymers and copolymerssuch as polytetrafluoroethylene), polycrystalline inorganic solidelectrolytes and/or combinations thereof. Electrolytes may compriselithium electrolyte salt(s) such as LiPF₆, LiBF₄, lithiumbis(oxalato)borate, LiN(CF₃SO₂)₂, LiN(C₂F₅SO₂)₂, LiAsF₆, LiC(CF₃SO₂)₃,LiClO₄, LiTFSI, LiB(C₂O₄)₂, LiBF₂(C₂O₄)), tris(trimethylsilyl)phosphite(TMSP), and combinations thereof. Ionic liquid(s) may be added to theelectrolyte as taught by WIPO Publication No. WO 2018/109774,incorporated herein by reference in its entirety. For example,electrolytes may comprise a large proportion, e.g., 10%, 20%, 30% ormore of VC and/or FEC as prominent cyclic carbonate compound, asdisclosed e.g., in U.S. Pat. No. 10,199,677, incorporated herein byreference in its entirety. In certain embodiments, electrolytes maycomprise linear solvent comprising at least one three-carbon and/orfour-carbon chain ester, cyclic carbonate solvent and at least onelithium salt, as disclosed e.g., in U.S. Patent Publication No.2019/0148774, incorporated herein by reference in its entirety.

In certain embodiments, the four-carbon chain ester may be representedby the structure of Formula (XVI):

whereinR⁴⁸ and R⁴⁹ are each independently alkyl, haloalkyl, cycloalkyl, aryl,heteroalicyclic, benzyl or heteroaryl;each of the alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzylor heteroaryl of R⁴⁸, or R⁴⁹ is optionally substituted with one or moreof alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,O—P(═O)(OR⁸)₂, trihalomethyl, cyano, S(═O)—R⁴⁸, S(═O)₂—R⁴⁸,S(═O)₂—NR⁴⁸R⁴⁹, halide, cycloalkyl, alkoxy, nitro, NR⁴⁸R⁴⁹, C(O)NR⁴⁸R⁴⁹,N(R⁴⁸)C(═O)—R⁴⁹, hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol,C(═O)—OR⁴⁸, C(═O)—R⁴⁸, aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) orany combination thereof; andn is an integer between 0 and 10.

In another embodiment, R⁴⁸ is a C₃-C₁₀ alkyl, C₃-C₂₀ alkyl or C₃-C₃₀alkyl. In another embodiment, R⁴⁸ is a C₄-C₁₀ alkyl, C₄-C₂₀ alkyl orC₄-C₃₀ alkyl. In another embodiment, the electrolyte is ethyl butyrateor butyl acetate.

In certain embodiments, the four-carbon chain ester may be representedby the structure of Formula (XVIa):

whereinR^(48′) is a C₃-C₁₀ alkyl, C₃-C₂₀ alkyl or C₃-C₃₀ alkyl;R⁴⁹ is alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl orheteroaryl;each of the alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzylor heteroaryl of R^(48′) or R⁴⁹ is optionally substituted with one ormore of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,O—P(═O)(OR⁴⁸)₂, trihalomethyl, cyano, S(═O)—R⁴⁹, S(═O)₂—R⁴⁸,S(═O)₂—NR⁴⁸R⁴⁹, halide, cycloalkyl, alkoxy, nitro, NR⁴⁸R⁴⁹, C(O)NR⁴⁸R⁴⁹,N(R⁴⁸)C(═O)—R⁴⁹, hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol,C(═O)—OR⁴⁸, C(═O)—R⁴⁸, aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) orany combination thereof;R⁴⁸ is alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl orheteroaryl; and n is an integer between 0 and 10.

In certain embodiments, the four-carbon chain ester may be representedby the structure of Formula (XVIb):

whereinR⁴⁸ is alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl orheteroaryl;R^(49′) is C₄-C₁₀ alkyl, C₄-C₂₀ alkyl or C₄-C₃₀ alkyl;each of the alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzylor heteroaryl of R⁴⁸ or R^(49′) is optionally substituted with one ormore of alkyl, haloalkyl, alkenyl, alkynyl, heteroalicyclic, heteroaryl,O—P(═O)(OR⁴⁸)₂, trihalomethyl, cyano, S(═O)—R⁴⁸, S(═O)₂—R⁴⁸,S(═O)₂—NR⁴⁸R⁴⁹, halide, cycloalkyl, alkoxy, nitro, NR⁴⁸R⁴⁹, C(O)NR⁴⁸R⁴⁹,N(R⁴⁸)C(═O)—R⁴⁹, hydroxy, alkylthiol, thiol, arylthiol, heteroarylthiol,C(═O)—OR⁴⁸, C(═O)—R⁴⁸, aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) orany combination thereof;R⁴⁹ is alkyl, haloalkyl, cycloalkyl, aryl, heteroalicyclic, benzyl orheteroaryl; andn is an integer between 0 and 10.

In certain embodiments, the four-carbon chain ester may be representedby the structure of Formula (XIa), Formula (XVIb), or any combinationthereof wherein Formula (XVIa) and Formula (XVIb) are describedhereinabove.

In certain embodiments, the cyclic carbonate may be represented by thestructure of Formula (XVII):

whereinR⁵⁰ and R⁵¹ are each independently H, alkyl, haloalkyl, alkenyl,alkynyl, cycloalkyl, aryl, heteroalicyclic heteroaryl, alkoxy, hydroxy,O—P(═O)(OR⁵⁰)₂, thiol, alkylthiol, aryloxy, heteroaryloxy, arylthiol,heteroarylthiol, nitro, halide, trihalomethyl, cyano, benzyl,C(O)NR⁵⁰R⁵¹, NR⁵⁰R⁵¹, N(R⁵⁰)C(═O)—R⁵¹, C(═O)—OR⁵⁰, S(═O)—R⁵⁰, S(═O)₂—R⁵⁰or S(═O)₂—NR⁵⁰R⁵¹;each of the alkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, aryl,benzyl, heteroaryl, heteroalicyclic, alkoxy, alkylthiol,heteroarylthiol, aryloxy, heteroaryloxy or arylthiol of R⁵⁰ or R⁵¹ isoptionally substituted with one or more of alkyl, haloalkyl, alkenyl,alkynyl, heteroalicyclic, heteroaryl, O—P(═O)(OR⁵⁰)₂, trihalomethyl,cyano, S(═O)—R⁵⁰, S(═O)₂—R⁵⁰, S(═O)₂—NR⁵⁰R⁵¹, halide, cycloalkyl,alkoxy, nitro, NR⁵⁰R⁵¹, C(O)NR⁵⁰R⁵¹, N(R⁵⁰)C(═O)—R⁵¹, hydroxy,alkylthiol, thiol, arylthiol, heteroarylthiol, C(═O)—OR⁵⁰, C(═O)—R⁵⁰,aryl, aryloxy, heteroaryloxy, (CH₂CH₂O)_(n+1) or any combinationthereof; andn is an integer between 0 and 10.

In another embodiment, the cyclic carbonate may be represented bycompound 123:

A range of experiments has been carried out with various electrolytesolution compositions and various additives. The baseline electrolytesolution comprises a solution of 30 wt % VC, 70 wt % four-carbon ester,1M LiPF₆ salt, without additives. The wt % is provided with respect tothe baseline electrolyte solution. Typically, in a non-limiting manner,the four-carbon ester included 1:1 ethyl butyrate, EB and butyl acetate,BA. The following modifications resulted in the following cyclinglifetime extensions (in percentage compared to the cycling lifetime withthe baseline electrolyte solution, which is designated as 100%):

A solution of 30 wt % VC, 70 wt % four-carbon ester, 1M LiPF₆ salt, witha RAFT RS460 additive (compound 1a) between 0.3-0.9 wt % to control SEIgrowth—resulting in cycling lifetime of 150% with respect to thebaseline solution.

A solution of 10 wt % VC, 90 wt % four-carbon ester, 1M LiPF₆ salt,without additional additives—resulting in cycling lifetime of 120% withrespect to the baseline solution.

A solution of 10 wt % VC, 90 wt % four-carbon ester, 1M LiPF₆ salt, witha RAFT RS460 additive (compound 1a) between 0.3-0.9 wt % to control SEIgrowth—resulting in cycling lifetime of 120% with respect to thebaseline solution.

A solution of 20 wt % VC, 90 wt % four-carbon ester, 1M LiPF₆ salt, witha RAFT RS460 additive (compound 1a) between 0.3-0.9 wt % to control SEIgrowth—resulting in cycling lifetime of 120% with respect to thebaseline solution.

A solution of 10 wt % VC, 90 wt % four-carbon ester, 1M LiPF₆ salt, witha RAFT RS549 (compound 35) between 0.3-0.9 wt % to control SEIgrowth—resulting in cycling lifetime of 170% with respect to thebaseline solution.

A solution of 30 wt % VC, 70 wt % four-carbon ester, 1M LiPF₆ salt, withadditives 1,3 propanesultone (PS) between 2.5-7.5 wt. % to reduceswelling at elevated temperatures, tertamilbenzene (t-AmB) between 0.5-5wt % to reduced side reaction at the cathode, and RAFT RS460 (compound1a) additive between 0.3-0.9 wt % to control SEI growth resulting incycling lifetime of 100% with respect to the baseline solution. It isnoted that additives t-AmB and RS460 (compound 1a) thus compensated forthe reduction in cycling lifetime known to be caused by PS that is usedto stabilize the SEI and reduce anode swelling.

A solution of 30 wt % VC, 70 wt % four-carbon ester, 1M LiPF₆ salt, witha RAFT RS549 (compound 35) additive between 0.3-0.9 wt % to control SEIgrowth—resulting in cycling lifetime of 170% with respect to thebaseline solution.

A solution of 30 wt % VC, 70 wt % four-carbon ester, 1M LiPF₆ salt, witha LiFOB additive between 1-5 wt % to reduce the side reaction at thecathode and a RAFT RS460 (compound 1a) additive between 0.3-0.9 wt % tocontrol SEI growth—resulting in cycling lifetime of 150% with respect tothe baseline solution.

A solution of 30 wt % VC, 70 wt % four-carbon ester, 1M LiPF₆ salt, witha Tertamilbenzene (t-AmB) additive between 0.5-5 wt % to reduce sidereaction at the cathode—resulting in cycling lifetime of 200% withrespect to the baseline solution.

It is noted that RAFT RS549 and RS460 are represented, respectively, by:

FIG. 6 is a high-level flowchart illustrating a method 100, according tosome embodiments of the invention. The method stages may be carried outwith respect to the disclosed electrolyte solution, which may optionallybe configured to implement method 100. Method 100 may comprise thefollowing stages, irrespective of their order.

Method 100 may comprise enhancing safety and performance of fastcharging lithium ion batteries (stage 105), for example by replacing atleast part of a linear solvent of an electrolyte solution with at leastone four-carbon chain ester (stage 110), e.g., as represented by thestructure of Formula (XIV), at a higher concentration than a cycliccarbonate solvent in the electrolyte solution (stage 117). Method 100may comprise using the at least one four-carbon chain ester as a mainlinear solvent of the electrolyte solution (stage 115), and using VC asa main cyclic carbonate solvent of the electrolyte solution (stage 120),with the VC being at a smaller weight percentage than the at least onefour-carbon chain ester. Method 100 may further comprise addingadditives, such as compound 1a, compound 35, LiFOB and/or t-AmB to theelectrolyte solution to increase the cycling lifetime of the batteries.

In some embodiments, any combination of the additives, solvents,electrolytes, lithium salts or any other ingredient as describedhereinabove can be employed within lithium ion batteries, electrolyticsolutions and methods of the present invention. In another embodiment, alinear solvent within the electrolytic solutions comprises at least onefour-carbon chain ester, represented by the structure of Formula (XVIa),Formula (XVIb) or any combination thereof as described above. In anotherembodiment, the solution further comprises compound 1a, compound 35,compound 36, LiFOB and/or tertamilbenzene (t-AmB). In anotherembodiment, an additive within the electrolytic solutions comprisestertamilbenzene (t-AmB:

the structure of Formula (I) as described above or any combinationthereof.

In another embodiment, an additive within the electrolytic solutionscomprises the structure of Formula (Ia), (Iai) or any combinationthereof where Formula (Ia) and (Iai) are described above. In anotherembodiment, an additive within the electrolytic solutions comprises thestructure of at least one of compound 1a, compound 35, compound 36,LiFOB and tertamilbenzene (t-AmB). In another embodiment, the solventwithin the solutions is a four-carbon chain ester solvent which isrepresented by the structure of Formula (XVIa), Formula (XVIb) or anycombination thereof where Formula (XVIa) and (XVIb) are described above.

Disclosed lithium ion batteries (and/or respective battery cellsthereof) may at least partly be configured, e.g., by selection ofmaterials, to enable operation at high charging and/or discharging rates(C-rate), ranging from 3-10 C-rate, 10-100 C-rate or even above 100C,e.g., 4C, 5C, 10C, 15C, 30C or more. It is noted that the term C-rate isa measure of charging and/or discharging of cell/battery capacity, e.g.,with 1C denoting charging and/or discharging the cell in an hour, and XC(e.g., 5C, 10C, 50C etc.) denoting charging and/or discharging the cellin 1/X of an hour—with respect to a given capacity of the cell.

In the above description, an embodiment is an example or implementationof the invention. The various appearances of “one embodiment”, “anembodiment”, “certain embodiments” or “some embodiments” do notnecessarily all refer to the same embodiments. Although various featuresof the invention may be described in the context of a single embodiment,the features may also be provided separately or in any suitablecombination. Conversely, although the invention may be described hereinin the context of separate embodiments for clarity, the invention mayalso be implemented in a single embodiment. Certain embodiments of theinvention may include features from different embodiments disclosedabove, and certain embodiments may incorporate elements from otherembodiments disclosed above. The disclosure of elements of the inventionin the context of a specific embodiment is not to be taken as limitingtheir use in the specific embodiment alone. Furthermore, it is to beunderstood that the invention can be carried out or practiced in variousways and that the invention can be implemented in certain embodimentsother than the ones outlined in the description above.

The invention is not limited to those diagrams or to the correspondingdescriptions. For example, flow need not move through each illustratedbox or state, or in exactly the same order as illustrated and described.Meanings of technical and scientific terms used herein are to becommonly understood as by one of ordinary skill in the art to which theinvention belongs, unless otherwise defined. While the invention hasbeen described with respect to a limited number of embodiments, theseshould not be construed as limitations on the scope of the invention,but rather as exemplifications of some of the preferred embodiments.Other possible variations, modifications, and applications are alsowithin the scope of the invention. Accordingly, the scope of theinvention should not be limited by what has thus far been described, butby the appended claims and their legal equivalents.

What is claimed is:
 1. A lithium ion battery comprising: at least oneanode comprising anode active material based on Si, Ge and/or Sn, atleast one cathode comprising cathode active material based on at leastone formulation comprising lithium iron-phosphorus (LFP) oxide orlithium metal oxide (LiMeO), wherein Me is one or more metal selectedfrom nickel, cobalt, manganese and aluminum and Li and O represent oneor more respective lithium and oxygen atoms, and electrolyte comprising:solvent comprising at least one linear carbonate and/or ester and atleast one cyclic carbonate and/or ester, at least one dissolved lithiumsalt, and at least one additive that is represented by at least one ofthe following compounds or their combinations:


2. The lithium ion battery of claim 1, comprising cathode activematerial based on at least one formulation comprising lithiumiron-phosphorus (LFP) oxide, lithium Nickel-Manganese-Cobalt (NMC)oxide, modified Li-NMC oxide and/or lithium Nickel Cobalt Aluminum oxide(NCA).
 3. The lithium ion battery of claim 1, wherein the solventcomprises: at least one of VC (vinylene carbonate), EC (ethylenecarbonate), PC (propylene carbonate), and FEC (fluoroethylenecarbonate), and at least one of DMC (dimethyl carbonate), DEC (diethylcarbonate), EMC (ethyl methyl carbonate), EB (ethyl butyrate) and BA(butyl acetate).